Constrained geometry addition polymerization catalysts

ABSTRACT

Metal complexes having constrained geometry and a process for preparation thereof, addition polymerization catalysts formed therefrom, processes for preparation of such addition polymerization catalysts, methods of use, and novel polymers formed thereby, including ElPE resins and pseudo-random copolymers, are disclosed and claimed.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This is a Divisional of the Continuation-in-part U.S. patentapplication Ser. No. 07/545,403, which is off the following U.S. patentapplication Ser. No.: 401,345, filed Aug. 31, 1989, now abandoned; Ser.No. 401,344, filed Aug. 31, 1989, now abandoned; Ser. No. 428,082, filedOct. 27, 1989; Ser. No. 428,283, filed Oct. 27, 1989, now abandoned;Ser. No. 428,276, filed Oct. 27, 1989, now abandoned; and Ser. No.520,168 filed Apr. 9, 1990, now abandoned, which is a continuation ofSer. No. 436,524, filed Nov. 14, 1989, now abandoned. The teachings ofall of the foregoing applications are incorporated herein in theirentireties by reference thereto.

BACKGROUND OF THE INVENTION

[0002] The present invention relates to metal coordination complexeshaving constrained geometry. The invention also relates to certain noveladdition polymerization catalysts comprising such metal complexes havingconstrained geometry. Furthermore, the invention relates to methods forthe polymerization of addition polymerizable monomers and to theresulting polymers.

[0003] Because of the unique exposure of the active metal site of themetal coordination complexes having constrained geometry, catalystsresulting therefrom have unique properties. Under certain conditions,the catalysts of the invention are capable of preparing novel olefinpolymers having previously unknown properties due to their unique facileabilities to polymerize α-olefins, diolefins, hindered vinylidenealiphatic monomers, vinylidene aromatic monomers and mixtures thereof.

[0004] Numerous metal coordination complexes are known in the artincluding such complexes involving monocyclopentadienyl groups andsubstituted monocyclopentadienyl groups. The present metal coordinationcomplexes differ from those previously known in the art due to the factthat the metal is bound to a delocalized substituted π-bonded moiety ina manner so as to induce a constrained geometry about the metal.Preferably the metal is bound to a cyclopentadienyl, substitutedcyclopentadienyl or similar group by both a η⁵-bond and a bridginglinkage including other ligands of the metal. The complexes alsopreferably include metals having useful catalytic properties.

[0005] Also previously known in the art are transition metalcoordination complexes known as tucked complexes. Such complexes aredescribed in Organometallics 6, 232-241 (1987).

[0006] In U.S. Ser. No. 8,800, filed Jan. 30, 1987 (published inequivalent form as EP 277,004) there are disclosed certainbis(cyclopentadienyl) metal compounds formed by reacting abis(cyclopentadienyl) metal complex with salts of Bronsted acidscontaining a noncoordinating compatible anion. The reference disclosesthe fact that such complexes are usefully employed as catalysts in thepolymerization of olefins. For the teachings contained therein U.S. Ser.No. 8,800 and EP 277,004 are herein incorporated in their entirety byreference thereto.

[0007] Previous attempts to prepare copolymers of vinylidene aromaticmonomers and α-olefins, in particular copolymers of styrene andethylene, have either failed to obtain substantial incorporation of thevinylidene aromatic monomer or else have achieved polymers of lowmolecular weight. In Polymer Bulletin, 20, 237-241 (1988) there isdisclosed a random copolymer of styrene and ethylene containing 1 molepercent styrene incorporated therein. The reported polymer yield was8.3×10⁻⁴ grams of polymer per micromole titanium employed.

[0008] It has now been discovered that previously known additionpolymerization catalysts are incapable of high activity andpolymerization of numerous monomers because they lack constrainedgeometry.

[0009] It would be desirable if there were provided novel complexes ofgroups 3 (other than scandium), 4-10 and the lanthamides havingconstrained geometry.

[0010] Additionally it would be desirable if there were provided novelcatalysts for addition polymerizations comprising novel complexes ofgroups 3 (other than scandium), 4-10 and the lanthamides havingconstrained geometry.

[0011] Furthermore, it would desirable if there were provided a processfor the preparation of polymers of addition polymerizable monomers usingnovel catalysts comprising complexes of groups 3 (other than scandium),4-10 and the lanthamides having constrained geometry.

[0012] Finally, it would be desirable if there were provided novelpolymers of addition polymerizable monomers that may be prepared by anaddition polymerization process using catalysts comprising novelcomplexes of groups 3 (other than scandium), 4-10 and the lanthamideshaving constrained geometry.

SUMMARY OF THE INVENTION

[0013] In one aspect the present invention relates to a metalcoordination complex having constrained geometry. More particularly itrelates to such coordination complexes that are usefully employed incombination with activating cocatalyst compounds or mixtures ofcompounds to form a catalytic system usefully employed in thepolymerization of addition polymerizable monomers, especiallyethylenically unsaturated monomers.

[0014] In another aspect the present invention relates to a process forpreparing certain components of the above metal coordination complexeshaving constrained geometry and to the precursor compounds necessarytherefor.

[0015] In yet another aspect the present invention relates to a processfor preparing addition polymers, especially homopolymers and copolymersof olefins, diolefins, hindered aliphatic vinyl monomers, vinylidenearomatic monomers and mixtures of the foregoing and to the resultingpolymer products.

[0016] According to the present invention there is provided a metalcoordination complex comprising a metal of group 3 (other thanscandium), 4-10 or the lanthamide series of the periodic table of theelements and a delocalized _-bonded moiety substituted with aconstrain-inducing moiety, said complex having a constrained geometryabout the metal atom such that the angle at the metal between thecentroid of the delocalized, substituted π-bonded moiety and the centerof at least one remaining substituent is less than such angle in asimilar complex containing a similar π-bonded moiety lacking in suchconstrain-inducing substituent, and provided further that for suchcomplexes comprising more than one delocalized, substituted π-bondedmoiety, only one thereof for each metal atom of the complex is a cyclic,delocalized, substituted π-bonded moiety.

[0017] In addition there is provided a metal coordination complexcorresponding to the formula:

[0018] wherein:

[0019] M is a metal of group 3 (other than scandium), 4-10, or thelanthamide series of the periodic table of the elements;

[0020] Cp* is a cyclopentadienyl or substituted cyclopentadienyl groupbound in an η⁵ bonding mode to M;

[0021] Z is a moiety comprising boron, or a member of group 14 of theperiodic table of the elements, and optionally sulfur or oxygen, saidmoiety having up to 20 non-hydrogen atoms, and optionally Cp* and Ztogether form a fused ring system;

[0022] X independently each occurrence is an anionic ligand group orneutral Lewis base ligand group having up to 30 non-hydrogen atoms;

[0023] n is 0, 1, 2, 3, or 4 depending on the valence of M; and

[0024] Y is an anionic or nonanionic ligand group bonded to Z and Mcomprising nitrogen, phosphorus, oxygen or sulfur and having up to 20non-hydrogen atoms, optionally Y and Z together form a fused ringsystem.

[0025] There is also provided according to the present invention aprocess for preparing a metal coordination complex corresponding to theforegoing formula I comprising the steps of:

[0026] A) contacting a metal compound of the formula MX_(n+2) or acoordinated adduct thereof with a dianionic salt compound correspondingto the formula:

(L^(+x))_(y)(Cp*-Z-Y)⁻²  (II)

or

((LX″)^(+x))_(y)(Cp*-Z-Y)⁻²  (III)

[0027] wherein:

[0028] L is a metal of group 1 or 2 of the periodic table of theelements,

[0029] X″ is fluoro, chloro, bromo, or iodo,

[0030] x and y are either 1 or 2 and the product of x and y equals 2,and

[0031] M, X, Cp, R, and Y are as previously defined; and

[0032] B) recovering the resulting product.

[0033] Further there is provided a process for preparing a metalcoordination complex corresponding to the foregoing formula I comprisingthe steps of:

[0034] A) contacting a metal compound of the formula MX_(n+1) or acoordinated adduct thereof with a dianionic salt compound correspondingto the formulas II or III;

[0035] B) oxidizing the metal to a higher oxidation state by contactingthe reaction product of step A) with a noninterfering oxidizing agent;and

[0036] C) recovering the resulting product.

[0037] There is also provided a catalyst useful in additionpolymerizations comprising the following components:

[0038] a) a metal coordination complex comprising a metal of group 3(other than scandium), 4-10 or the lanthamide series of the periodictable of the elements and a delocalized π-bonded moiety substituted witha constrain-inducing moiety, said complex having a constrained geometryabout the metal atom such that the angle at the metal between thecentroid of the delocalized, substituted π-bonded moiety and the centerof at least one remaining substituent is less than such angle in asimilar complex containing a similar π-bonded moiety lacking in suchconstrain-inducing substituent, and provided further that for suchcomplexes comprising more than one delocalized, substituted π-bondedmoiety, only one thereof for each metal atom of the complex is a cyclic,delocalized, substituted π-bonded moiety; and

[0039] b) an activating cocatalyst.

[0040] In a further embodiment of the present invention there isprovided a catalyst useful in addition polymerizations comprising thefollowing components:

[0041] a) a metal coordination complex corresponding to the formula I,and

[0042] b) an activating cocatalyst.

[0043] Even further according to the present invention there is provideda polymerization process comprising contacting one or more additionpolymerizable monomers under addition polymerization conditions with acatalyst comprising:

[0044] a) a metal coordination complex comprising a metal of group 3(other than scandium), 4-10 or the lanthamide series of the periodictable of the elements and a delocalized π-bonded moiety substituted witha constrain-inducing moiety, said complex having a constrained geometryabout the metal atom such that the angle at the metal between thecentroid of the delocalized, substituted π-bonded moiety and the centerof at least one remaining substituent is less than such angle in asimilar complex containing a similar π-bonded moiety lacking in suchconstrain-inducing substituent, and provided further that for suchcomplexes comprising more than one delocalized, substituted π-bondedmoiety, only one thereof for each metal atom of the complex is a cyclic,delocalized, substituted π-bonded moiety; and

[0045] b) an activating cocatalyst.

[0046] Further according to the present invention there is provided anaddition polymerization process comprising the steps of;

[0047] A) contacting a mixture comprising one or more additionpolymerizable monomers under polymerization conditions in the presenceof a catalyst comprising a metal coordination complex corresponding tothe formula I and an activating cocatalyst; and

[0048] B) recovering the resulting polymer.

[0049] Further still according to the present invention there isprovided a polymer comprising in interpolymerized form one or moreaddition polymerizable monomers prepared by contacting an additionpolymerizable monomer or mixture thereof under addition polymerizationconditions with a catalyst comprising:

[0050] a) a metal coordination complex comprising a metal of group 3(other than scandium), 4-10 or the lanthamide series of the periodictable of the elements and a delocalized π-bonded moiety substituted witha constrain-inducing moiety, said complex having a constrained geometryabout the metal atom such that the angle at, the metal between thecentroid of the delocalized, substituted π-bonded moiety and the centerof at least one remaining substituent is less than such angle in asimilar complex containing a similar π-bonded moiety lacking in suchconstrain-inducing substituent, and provided further that for suchcomplexes comprising more than one delocalized, substituted π-bondedmoiety, only one thereof for each metal atom of the complex is a cyclic,delocalized, substituted π-bonded moiety; and

[0051] b) an activating cocatalyst.

[0052] In a still further embodiment of the present invention there isprovided a polymer comprising in polymerized form one or more additionpolymerizable monomers prepared by contacting an addition polymerizablemonomer or mixture thereof under addition polymerization conditions witha catalyst comprising the following components:

[0053] a) a metal coordination complex corresponding to the formula Iand an activating cocatalyst.

[0054] In still further embodiments there are provided ElPE polymerswhich are highly elastic, interpolymers of ethylene and one or moreolefins other than ethylene.

[0055] In addition there are provided pseudo-random interpolymers of anα-olefin, particularly ethylene and a vinylidene aromatic monomer, ahindered aliphatic vinylidene monomer, or a mixture thereof.

[0056] The complexes of the invention are usefully employed as catalystsfor addition polymerization processes to prepare polymers that areuseful as molded articles, films for packaging applications, and foamsfor cushioning applications; and in the modification of synthetic andnaturally occuring resins. The complexes may also be used as catalystsfor hydrogenations, catalytic cracking processes, and in otherindustrial applications.

DESCRIPTION OF THE DRAWINGS

[0057] FIGS. 1-5 are computer generated models of constrained geometrycomplexes of the invention based on single crystal X-ray data.

[0058]FIGS. 6 and 7 are computer generated models of metal complexesbased on single crystal X-ray data showing less constrain than those ofFIGS. 1-5.

[0059] FIGS. 8-13 illustrate calculated and observed distribution ofstyrene, ethylene and reversed styrene units in ethylene/styrenecopolymers observing pseudo-random incorporation rules according to theinvention.

[0060]FIG. 14 illustrates lack of agreement between calculated andobserved distribution of styrene, ethylene and reversed styrene units inethylene/styrene copolyers if completely random incorporation rules arefollowed.

[0061]FIG. 15 shows typical rheology curves of a ElPE resin according tothe present invention. Shown are complex viscosity, η*, and tan δ curvesas a function of shear rate, for the resin.

[0062]FIG. 16 shows a typical curve of elastic modulus versus melt indexfor the ElPE resins of the present invention.

[0063]FIG. 17 shows typical rheology curves of a conventionally preparedpolyethylene resin. Shown are complex viscosity, η*, and tan δ curves asa function of shear rate, for the resin.

DETAILED DESCRIPTION OF THE INVENTION

[0064] By use of the term “delocalized π-bonded moiety” is meant anunsaturated organic moiety, such as those comprising ethylenic oracetylenic functionality, wherein the π-electrons thereof are donated tothe metal to form a bond. Examples include alkene-, alkenyl-, alkyne-,alkynyl-, allyl-, polyene-, and polyenyl moieties as well as unsaturatedcyclic systems.

[0065] By use of the term “constrained geometry” herein is meant thatthe metal atom is forced to greater exposure of the active metal sitebecause of one or more substituents on the delocalized π-bonded moiety.Preferably the delocalized π-bonded moiety is a cyclopentadienyl orsubstituted cyclopentadienyl group forming a portion of a ring structurewherein the metal is both bonded to an adjacent covalent moiety and isheld in association with the delocalized π-bonded moiety through η⁵bonds. It is understood that each respective bond between the metal atomand the constituent atoms of the delocalized π-bonded moiety need not beequivalent. That is the metal may be symetrically or unsymetricallyπ-bound to the π-bonded moiety.

[0066] The geometry of the active metal site is further defined asfollows. The centroid of the π-bonded moiety may be defined as theaverage of the respective X, Y, and Z coordinates of the atomic centersforming the π-bonded moiety. The angle, Θ, formed at the metal centerbetween the centroid of the π-bonded moiety and each other ligand of themetal complex may be easily calculated by standard techniques of singlecrystal X-ray diffraction. Each of these angles may increase or decreasedepending on the molecular structure of the constrained geometry metalcomplex. Those complexes wherein one or more of the angles, Θ, is lessthan in a similar, comparative complex differing only in the fact thatthe constrain-inducing substituent is replaced by hydrogen haveconstrained geometry for purposes of the present invention. Preferablyone or more of the above angles, Θ, decrease by at least 5% morepreferably 7.5% compared to the comparative complex. Highly preferably,the average value of all bond angles, Θ, is also less than in thecomparative complex. Most preferably the metal coordination complexhaving constrained geometry is in the form of a ring structure, i.e. theconstrain-inducing substituent is part of a ring system which includesthe metal.

[0067] Preferably, monocyclopentadienyl metal coordination complexes ofgroup 4 or lanthamide metals according to the present invention haveconstrained geometry such that the smallest angle, Θ, is less than 115°,more preferably less than 110°, most preferably less than 105°.

[0068] Illustrative atomic arrangements of complexes as determined fromsingle crystal X-ray diffraction values are shown in FIGS. 1-7.

[0069]FIG. 1 shows the single-crystal X-ray crystallographicallydetermined structure of(4-methylphenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride. The angle formed by the centroid of the cyclopentadienylring (C2, C3, C5, C7 and C9), the titanium atom (TI1), and the nitrogenatom (N14) is 105.7°.

[0070]FIG. 2 shows the single-crystal X-ray crystallographicallydetermined structure of (t-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dimethyl.The angle formed by the centroid of the cyclopentadienyl ring (C2, C3,C3*, C5, and C5*), the zirconium atom (ZR1), and the nitrogen atom (N9)was determined to be 102.0°.

[0071]FIG. 3 shows the single-crystal X-ray crystallographicallydetermined structure of (phenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride. The angle formed by the centroid of the cyclopentadienylring (C2, C3, C5, C7, and C9), the titanium atom (TI1), and the nitrogenatom (N14) was determined to be 106.1°.

[0072]FIG. 4 shows the single-crystal X-ray crystallographicallydetermined structure of (tert-butylamido)dimethyl(η⁵-cyclopentadienyl)silanezirconium dichloride. Thestructure shows that this molecule crystallizes as a dimer with 2bridging chlorides. The angle formed by the centroid of thecyclopentadienyl ring (C2, C3, C4, C5, and C6), the zirconium atom(ZR1), and the nitrogen atom (N10), or the angle formed by the centroidof the cyclopentadienyl ring (C102, C103, C104, C105, and C106), thezirconium atom (ZR101), and the nitrogen atom (N110) were determined tobe 99.1°.

[0073]FIG. 5 shows the single-crystal X-ray crystallographicallydetermined structure of (t-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdichloride. The angle formed by the centroid of the cyclopentadienylring (C1, C2, C3, C4, and C5), the zirconium atom (ZR), and the nitrogenatom (N) was determined to be 102.0°.

[0074]FIG. 6 shows the single-crystal X-ray crystallographicallydetermined structure of (t-butylamido)tetramethyl(tetramethyl-η⁵-cyclopentadienyl)disilanezirconiumdichloride. The relatively long disilyl linking group that connects thecyclopentadienyl ring to the nitrogen atom of the amide ligand allowsthe nitrogen atom to be less constrained. The angle formed by thecentroid of the cyclopentadienyl ring (C2, C3, C5, C7, and C9), thezirconium atom (ZR1), and the nitrogen atom (N17) was determined to be118.0°. The activity of this catalyst towards olefin polymerization isconsiderably diminished relative to the analogous monosilane linkinggroup in (tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdichloride (FIG. 5).

[0075]FIG. 7 shows the single-crystal X-ray crystallographicallydetermined structure of (t-butylamido)tetramethyl(tetramethyl-η⁵-cyclopentadienyl)disilanetitaniumdichloride. The relatively long disilyl linking group that connects thecyclopentadienyl ring to the nitrogen atom of the amide ligand allowsthe nitrogen atom to be less constrained. The angle formed by thecentroid of the cyclopentadienyl ring (C2, C3, C5, C7, and C9), thetitanium atom (TI1), and the nitrogen atom (N17) was determined to be120.5°. Accordingly, the activity of this catalyst towards olefinpolymerization is considerably diminished relative to the analogousmonosilane linking group in (t-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride.

[0076] The term “activating cocatalyst” as used herein refers to asecondary component of the catalyst able to cause the metal-containingcomplex to become effective as an addition polymerization catalyst oralternatively to balance the ionic charge of a catalytically activatedspecies. Examples of the foregoing activating cocatalysts for use hereininclude aluminum compounds containing an Al—O bond such as thealkylaluminoxanes, especially methylaluminoxane; aluminum alkyls;aluminum halides; aluminum alkylhalides; Lewis acids; ammonium salts;noninterfering oxidizing agents, i.e. silver salts, ferrocenium ions,etc.; and mixtures of the foregoing.

[0077] Particular techniques for the preparation of aluminoxane typecompounds are disclosed in U.S. Pat. No. 4,542,119 the teachings ofwhich are incorporated herein in their entirety by reference thereto. Ina particularly preferred embodiment an aluminum alkyl compound iscontacted with a regeneratable water-containing substance such ashydrated alumina, silica, or other substance. A process for preparingaluminoxane employing such regeneratable substance is disclosed incopending application Ser. No. 91,566, filed Aug. 31, 1987 and assignedto the same assignee as the present patent application.

[0078] Additional suitable activating cocatalysts include compoundscorresponding to the formula:

A1R_(n)X″_(3−n)

[0079] wherein:

[0080] R is each occurrence C₁₋₁₀ alkyl or aralkyl;

[0081] X″ is as previously defined; and

[0082] n is 1, 2 or 3.

[0083] Most preferably such cocatalysts are trialkyl aluminum compounds,particularly triethyl aluminum. “Addition polymerizable monomers”include for example ethylenically unsaturated monomers, acetyleniccompounds, conjugated or nonconjugated dienes, polyenes, carbonmonoxide, etc. Preferred monomers include the C₂₋₁₀ α-olefins especiallyethylene, propylene, isobutylene, 1-butene, 1-hexene,4-methyl-1-pentene, and 1-octene. Other preferred monomers includestyrene, halo- or alkyl substituted styrene, vinyl chloride,acrylonitrile, methylmethacrylate, tetrafluoroethylene,methacrylonitrile, vinylidene chloride, vinylbenzocyclobutane, and1,4-hexadiene.

[0084] By the term “hindered aliphatic vinylidene compounds” is meantaddition polymerizable vinylidene monomers corresponding to the formula:

CG₂=CG′R″

[0085] wherein R″ is an sterically bulky, aliphatic substituent of up to20 carbons, G independently each occurrence is hydrogen or methyl, andG′ independently each occurrence is hydrogen or methyl or alternativelyG′ and R″ together form a ring system. By the term “sterically bulky” ismeant that the monomer bearing this substituent is normally incapable ofaddition polymerization by standard Ziegler-Natta polymerizationcatalysts at a rate comparable with ethylene polymerizations. Preferredhindered aliphatic vinylidene compounds are monomers in which one of thecarbon atoms bearing ethylenic unsaturation is tertiary or quaternarysubstituted. Examples of such substituents include cyclic aliphaticgroups such as cyclohexane, cyclohexene, cyclooctene, or ring alkyl oraryl substituted derivatives thereof, tert-butyl, norbornyl, etc. Mostpreferred hindered aliphatic vinylidene compounds are the variousisomeric vinyl-ring substituted derivatives of cyclohexene andsubstituted cyclohexenes, and 5-ethylidene-2-norbornene. Especiallysuitable are 1-, 3-, and 4-vinylcyclohexene.

[0086] By the term “hindered vinylidene compound” is meant additionpolymerizable vinylidene monomers corresponding to the formula:

CG₂=CGR″

[0087] wherein R′″ is R″ or an aryl substituent of up to 20 carbons, andG and G′ are as previously defined. For example, in addition to hinderedaliphatic vinylidene compounds, hindered vinylidene compounds alsoinclude the vinylidene aromatic monomers.

[0088] By the term “vinylidene aromatic monomers” is meant additionpolymerizable compounds corresponding to the formula:

CG₂-C(G)-Ph

[0089] wherein G independently each occurrence is hydrogen or methyl andPh is phenyl, or a halo- or C₁₋₄ alkyl-substituted phenyl group.Preferred vinylidene aromatic monomers are monomers corresponding to theabove formula wherein G each occurrence is hydrogen. A most preferredvinylidene aromatic monomer is styrene.

[0090] By the term “α-olefin” is meant ethylene and the C₃₋₁₀ olefinshaving ethylenic unsaturation in the α-position. Preferred α-olefins areethylene, propylene, 1-butene, isobutylene, 4-methyl-1-pentene,1-hexene, and 1-octene, and mixtures thereof.

[0091] As used herein all reference to the Periodic Table of theElements and groups thereof shall be to the version of the tablepublished by the Handbook of Chemistry and Physics, CRC Press, 1987,utilizing the IUPAC system for naming groups.

[0092] Preferred metal coordination complexes are group 4 or Lanthamidebased complexes. Further preferred complexes are those comprising adelocalized η⁵-bonded group which is a cyclopentadienyl or substitutedcyclopentadienyl group which forms a ring structure with the metal atom.Preferred delocalized η-bonded moieties are cyclopentadienyl-, indenyl-and fluorenyl groups, and saturated derivatives thereof which form aring structure with the metal atom. Each carbon atom in thecyclopentadienyl radical may be unsubstituted or substituted with thesame or a different radical selected from the group consisting ofhydrocarbyl radicals, substituted-hydrocarbyl radicals wherein one ormore hydrogen atoms is replaced by a halogen atom,hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from Group 14 of the Periodic Table of the Elements, andhalogen radicals. In addition two or more such substituents may togetherform a fused ring system. Suitable hydrocarbyl andsubstituted-hydrocarbyl radicals, which may replaceat least one hydrogenatom in the cyclopentadienyl radical, will contain from 1 to about 20carbon atoms and include straight and branched alkyl radicals, cyclichydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals,aromatic radicals and alkyl-substituted aromatic radicals. Suitableorganometalloid radicals include mono-, di- and trisubstitutedorganometalloid radicals of Group 14 elements wherein each of thehydrocarbyl groups contain from 1 to about 20 carbon atoms. Moreparticularly, suitable organometalloid radicals include trimethylsilyl,triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl,phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl,triphenylgermyl, trimethylgermyl and the like.

[0093] In the previously disclosed Formula I, suitable anionic ligandgroups, X, are illustratively selected from the group consisting ofhydride, halo, alkyl, silyl, germyl, aryl, amide, aryloxy, alkoxy,phosphide, sulfide, aceyl, pseudo halides such as cyanide, azide, etc.,acetylacetonate, etc., or a combination thereof.

[0094] As previously mentioned, the complexes according to the presentinvention preferably comprise structures having altered or enhancedcatalytic activity at the metal site when the complex is combined with acocatalyst. In this regard electron donating substituents have beenfound to improve the catalytic properties of the complexes. That is,even though certain of the complexes do not possess constrainedgeometry, the same never-the-less possess catalytic properties, alone orin combination with activating substances.

[0095] A highly preferred metal coordination complex corresponds to theformula:

[0096] wherein R′ each occurrence is independently selected from thegroup consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, haloand combinations thereof having up to 20 non-hydrogen atoms;

[0097] X each occurrence independently is selected from the groupconsisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy,alkoxy, amide, siloxy, neutral Lewis base ligands and combinationsthereof having up to 20 non-hydrogen atoms;

[0098] Y is —O—, —S—, —NR*—, —PR* —, or a neutral two electron donorligand selected from the group consisting of OR*, SR*, NR*₂, or PR*₂;

[0099] M is a previously defined; and

[0100] Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂,GeR*₂, BR*, or BR*₂; wherein:

[0101] R* each occurrence is independently selected from the groupconsisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl,halogenated aryl groups, and mixtures thereof, said R* having up to 20non-hydrogen atoms or two or more R* groups from Y, Z, or both Y and Zform a fused ring system.

[0102] It should be noted that whereas formula I and the followingformulas indicate a cyclic structure for the catalysts, when Y is aneutral two electron donor ligand, the bond between M and Y is moreaccurately referred to as a coordinate-covalent bond. Also, it should benoted that the complex may exist as a dimer or higher oligomer.

[0103] Further preferably, at least one of R′, Z, or R* is an electrondonating moiety. Thus, highly preferably Y is a nitrogen or phosphoruscontaining group corresponding to the formula —N(R″″)— or —P(R″″)—,wherein R″″ is C₁₋₁₀ alkyl or aryl, i.e. an amido or phosphido group.

[0104] Most highly preferred complex compounds are amidosilane- oramidoalkanediyl-compounds corresponding to the formula:

[0105] wherein:

[0106] M is titanium, zirconium or hafnium, bound in an η⁵-bonding modeto the cyclopentadienyl group;

[0107] R′ each occurrence is independently selected from the groupconsisting of hydrogen, silyl, alkyl, aryl and combinations thereofhaving up to 10 carbon or silicon atoms;

[0108] E is silicon or carbon;

[0109] X independently each occurrence is hydride, halo, alkyl, aryl,aryloxy or alkoxy of up to 10 carbons;

[0110] m is 1 or 2; and

[0111] n is 1 or 2 depending on the valence of M.

[0112] Examples of the above most highly preferred metal coordinationcompounds include compounds wherein the R′ on the amido group is methyl,ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl,benzyl, phenyl, etc.; the cyclopentadienyl group is cyclopentadienyl,indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, etc.; R′ onthe foregoing cyclopentadienyl groups each occurrence is hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers),norbornyl, benzyl, phenyl, etc.; and X is chloro, bromo, iodo, methyl,ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl,benzyl, phenyl, etc. Specific compounds include:(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdichloride,(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdichloride,(methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdichloride,(methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdichloride,(ethylamido)(tetramethyl-η⁵-cyclopentadienyl)-methylenetitaniumdichloro,(tert-butylamido)dibenzyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdibenzyl,(benzylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride,(phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdibenzyl, and the like.

[0113] The complexes are prepared by contacting the metal reactant and aGroup I metal derivative or Grignard derivative of the cyclopentadienylcompound in a solvent and separating the salt byproduct. Suitablesolvents for use in preparing the metal complexes are aliphatic oraromatic liquids such as cyclohexane, methylcyclohexane, pentane,hexane, heptane, tetrahydrofuran, diethyl ether, benzene, toluene,xylene, ethylbenzene, etc., or mixtures thereof.

[0114] In a preferred embodiment, the metal compound is MX_(n+1), i.e. Mis in a lower oxidation state than in the corresponding compound,MX_(n+2) and the oxidation state of M in the desired final complex. Anoninterfering oxidizing agent may thereafter be employed to raise theoxidation state of the metal. The oxidation is accomplished merely bycontacting the reactants utilizing solvents and reaction conditions usedin the preparation of the complex itself. By the term “non interferingoxidizing agent” is meant a compound having an oxidation potentialsufficient to raise the metal oxidation state without interfering withthe desired complex formation or subsequent polymerization processes. Aparticularly suitable noninterfering oxidizing agent is AgCl.

[0115] In order to assist in the handling of the metal compoundsemployed in the present process corresponding to the formula MX_(n+2),it may be beneficial first to form a solid adduct thereof by the use ofa suitable coordinating agent according to well known techniques in theart. For example, whereas titanium tetrachloride is a fuming liquidwhich is difficult to handle, one may first form an adduct of TiCl₄ withan ether, tertiary amine, tertiary phosphine or other basic nonproticcompound. The resulting solids may be more easily handled. A preferredcoordinating adduct is tetrahydrofuran.

[0116] The reactions employed in preparing the metal complex may beconducted either heterogeneously or homogeneously. That is, the variousreactants or the resulting product need not be substantially soluble inthe solvent mixture. Generally the reactants are contacted under aninert atmosphere for a time from several minutes to several days.Agitation may be employed if desired. The temperature of the reaction isgenerally from −90° C. to 150° C., preferably from −20° C. to 70° C.

[0117] Suitable catalysts for use according to the present invention areprepared by combining the metal coordination compound and activatingcocatalyst compound in any order and in any suitable manner. Preferablythe ratio of the coordination complex and cocatalyst on a molar basis isfrom about 1:0.1 to about 1:10,000. It will, of course, be appreciatedthat the catalyst system may also be formed in situ if the componentsthereof are added directly to the polymerization process and a suitablesolvent or diluent, including condensed monomer, is used in saidpolymerization process. Suitable solvents include toluene, ethylbenzene,alkanes and mixtures thereof. In certain cases the catalysts may beisolated from solution and retained under inert atmosphere prior to use.The catalysts' components are sensitive to both moisture and oxygen andshould be handled and transferred in an inert atmosphere such asnitrogen, argon or helium or under vacuum.

[0118] The polymerization is conducted according to known techniques forZiegler-Natta or Kaminsky-Sinn type polymerizations. That is, themonomer(s) and catalyst are contacted at a temperature from −30° C. to250° C., at reduced, elevated or atmospheric pressures. Thepolymerization is conducted under an inert atmosphere which may be ablanketing gas such as nitrogen, argon, hydrogen, ethylene, etc. orunder vacuum. Hydrogen may additionally be utilized in the control ofmolecular weight through chain termination as is previously known in theart. The catalyst may be used as is or supported on a suitable supportsuch as alumina, MgCl₂ or silica to provide a heterogeneous supportedcatalyst. A solvent may be employed if desired. Suitable solventsinclude toluene, ethylbenzene, and excess vinylidene aromatic or olefinmonomer. The reaction may also be conducted under solution or slurryconditions, in a suspension utilizing a perfluorinated hydrocarbon orsimilar liquid, in the gas phase, i.e. utilizing a fluidized bedreactor, or in a solid phase powder polymerization. A catalyticallyeffective amount of the present catalyst and cocatalyst are any amountsthat successfully result in formation of polymer. Such amounts may bereadily determined by the routine experimentation by the skilledartisan. Preferred amounts of catalyst and cocatalyst are sufficient toprovide an equivalent ratio of addition polymerizable monomer:catalystof from 1×10¹⁰:1 to 100:1, preferably from 1×10⁸:1 to 500:1, mostpreferably 1×10⁶:1 to 1000:1. The cocatalyst is generally utilized in anamount to provide an equivalent ratio of cocatalyst:catalyst from10,000:1 to 0.1:1, preferably from 1,000:1 to 1:1.

[0119] It is to be understood that the metal complex may undergo varioustransformations or form intermediate species prior to and during thecourse of a polymerization. Thus other precursors could possibly beconceived to achieve the same catalytic species as are herein envisionedwithout departing from the scope of the present invention.

[0120] The resulting polymeric product is recovered by filtering orother suitable technique. Additives and adjuvants may be incorporated inthe polymers of the present invention in order to provide desirablecharacteristics. Suitable additives include pigments, UV stabilizers,antioxidants, blowing agents, lubricants, plasticizers,photosensitizers, and mixtures thereof.

[0121] In the preparation of copolymers containing vinylidene aromaticor hindered aliphatic vinyl monomers it is desirable that a comonomerthat is an α-olefin that is not particularly sterically hindered also beemployed. Without wishing to be bound by any particular theory ofoperation, it is believed this is because the active site becomescrowded with the incorporation of the hindered vinyl compound making itunlikely that another hindered vinyl compound could enter into thepolymerization as the next monomer in the sequence. After theincorporation of one or more olefins other than a hindered vinylcompound the active site once again becomes available for inclusion of ahindered vinyl monomer. On a limited basis however, thevinylidenearomatic monomer or sterically hindered vinyl monomer mayinsert into the polymer chain in reverse order, i.e. so as to result intwo methylene groups between the substituted polymer backbone moiety.

[0122] Preferably such polymers possess a Mw of greater than 13,000,more preferably greater than 20,000 and most preferably greater than30,000. Also preferably such polymers possess a melt index (I₂), ASTMD-1238 Procedure A, condition E, of less than 125, more preferably from0.01-100 and most preferably from 0.1 to 10.

[0123] Due to the use of the previously mentioned catalyst systemcomprising a coordination complex having constrained geometry,copolymers may be prepared that incorporate relatively bulky or hinderedmonomers in substantially random manner at low concentrations, and athigher concentrations according to an ordered insertion logic. Thecopolymers of a-olefins, especially ethylene and a hindered aliphaticvinylidene compound or vinylidene aromatic monomer can further bedescribed as “pseudo-random”. That is, the copolymers lack well definedblocks of either monomer, however the respective monomers are limited toinsertion according to certain rules.

[0124] These rules were deduced from certain experimental detailsresulting from an analysis of the polymers. The polymers were analyzedby ¹³C NMR spectroscopy at 130° C. with a Varian VXR-300 spectrometer at75.4 MHz. Samples of 200 to 250 mg polymer were dissolved in 15 mL ofhot o-dichlorobenzene/1,1,2,2-tetrachloroethane-d₂ (approximately 70/30,v/v) which was approximately 0.05 M in chromium (III)tris(acetylacetonate) and a portion of the resulting solution was addedto a 10 mm NMR tube. The following parameters and conditions were used:spectral width, 16,500 Hz; acquisition time 0.090 s; pulse width, 36°;delay, 1.0 s with the decoupler gated off during the delay,; FT size32K; number of scans, >30,000; line broadening, 3 Hz. Spectra, asrecorded were referenced to tetrachloroethane-d₂ (δ 73.77 ppm, TMSscale).

[0125] Therefor, without wishing to be bound by any particular theory,the results of the foregoing experimental procedures indicate that aparticular distinguishing feature of pseudo-random copolymers is thefact that all phenyl or bulky hindering groups substituted on thepolymer backbone are separated by 2 or more methylene units. In otherwords, the polymers comprising a hindered monomer of the presentinvention can be described by the following general formula (usingstyrene as the hindered monomer for illustration):

[0126] where j, k, and l≧1

[0127] In further explanation of the foregoing experimental andtheoretical results, and without wishing to be bound by any particulartheory it can be concluded that during the addition polymerizationreaction employing the present catalysts, if a hindered monomer isinserted into the growing polymer chain, the next monomer inserted mustbe ethylene or a hindered monomer which is inserted in an inverted or“tail-to-tail” fashion. This is illustrated below for a hindered vinylmonomer where M is the catalyst metal center, HG is a hindering group,and P is the growing polymer chain:

[0128] During the polymerization reaction, ethylene may be inserted atany time. After an inverted or “tail-to-tail” hindered monomerinsertion, the next monomer must be ethylene, as the insertion ofanother hindered monomer at this point would place the hinderingsubstituent closer together than the minimum separation as describedabove. A consequence of these polymerization rules is the catalysts ofthis invention do not homopolymerize styrene to any appreciable extent,while a mixture of ethylene and styrene is rapidly polymerized and maygive high styrene content (up to 50 mole % styrene) copolymers.

[0129] As a further illustration of the description of theα-olefin/hindered monomer copolymer of the present invention, a computermodel of the polymerization reaction was used to calculate the expected¹³C NMR spectrum of the polymer product. The computer program utilized arandom number generator to select either α-olefin or hindered monomer tobe inserted into a growing polymer chain, then calculated the number ofeach type of ¹³C NMR signals resulting from that insertion. Polymerswere computer generated by repeating this process for 10,000 or moremonomer insertions, and the resulting calculated ¹³C NMR spectrum wascompared to actual experimental ¹³C NMR spectra for pseudo-randomethylene/styrene copolymers of the invention.

[0130] Computer simulations of the polymer and resulting ¹³C NMR spectraof the calculated pseudo-random ethylene/styrene copolymers wereperformed using the constraint that if styrene monomer were insertedinto the growing polymer chain, the next monomer inserted must beethylene or a styrene which is inserted in an inverted or “tail-to-tail”fashion. Optimum fits between experimental and calculated spectra wereobtained if approximately 15% of the styrene insertions are in the“tail-to-tail” manner. The observed and calculated ¹³C NMR spectra forsuch pseudo-random ethylene/styrene copolymers containing 1.4, 4.8, 9.0,13, 37, and 47 mole percent styrene are shown in FIGS. 8-13. In eachcase, the observed and calculated spectra are in excellent agreement.

[0131] Computer simulation of the polymer and resulting ¹³C NMR spectraof completely random α-olefin/hindered monomer copolymers were thenperformed using no constraints on hindered monomer insertion. In otherwords, the hindered monomer was allowed to insert into the growingpolymer chain after a previous hindered monomer insertion if the randomnumber generator selected hindered monomer as the next monomer to beinserted. The calculated spectra for these completely random copolymersdo not agree with the observed ¹³C NMR spectra, as shown in FIG. 14 fora 37 mole percent styrene containing ethylene/styrene copolymer.

[0132] Prior to polymerization according to the present process themonomers and solvents, if any, may be purified by vacuum distillation,and/or contacted with molecular sieves, silica, or alumina to removeimpurities. In addition, reactive blanking agents, such astrialkylaluminum compounds, alkali metals and metal alloys, especiallyNa/K, may be used to remove impurities.

[0133] Suitable vinylidenearomatic monomers which may be employedaccording to the present invention include styrene as well as α-methylstyrene, the lower alkyl- or phenyl- ring substituted derivatives ofstyrene, such as ortho-, meta-, and para-methylstyrene, or mixturesthereof, the ring halogenated styrenes, vinylbenzocyclobutanes, anddivinylbenzene. A preferred vinylidenearomatic monomer is styrene.

[0134] In the polymerization of vinylidenearomatic monomers or hinderedaliphatic vinylidene compounds and olefins the monomers are preferablycombined in a proportion so as to achieve a vinylidenearomatic monomer(or hindered aliphatic vinylidene compound) content of at least 1.0 molepercent in the resulting polymer more preferably from 1.5 to less than50 mole percent, highly preferably 5.0 to 48 mole percent, and mostpreferably from more than 8.0 up to 47 mole percent. Preferred operatingconditions for such polymerization reactions are pressures fromatmospheric to 1000 atmospheres and temperatures from 30° C. to 200° C.Polymerizations at temperatures above the autopolymerization temperatureof the respective monomers may contain small amounts of homopolymerpolymerization products resulting from free radical polymerization.

[0135] Certain of the polymers prepared according to the presentinvention, especially copolymers of ethylene and an α-olefin other thanethylene, are characterized by unique rheological properties. Inparticular, it has been found that the polymers (hereinafter calledElastic Polyethylenes or ElPEs) are less Newtonian than conventionallyprepared linear polyethylene resins of similar olefin content. Thepolymers also have higher elastic modulus particularly at high meltindices compared to such conventional polymers. This property makes theresin especially useful in the formation of films, foams and fabricatedarticles, for example by blow molding techniques. The above phenomenonis more particularly defined by reference to FIG. 16 wherein complexviscosity, η* measured in poise at 190° C., is plotted as a function ofshear rate, ω, measured in radians per second for a typical ElPEcopolymer of ethylene and 1-octene according to the invention. The slopeof this curve indicates the melt is highly non-Newtonian. The actualvalues of η* and ω utilized in the graph are: η* ω η* ω η* ω 1.962 × 10⁵0.01000 3.230 × 10⁴ 0.2512 1.088 × 10⁴ 6.310 1.511 × 10⁵ 0.01585 2.713 ×10⁴ 0.3981 9.336 × 10³ 10.000 1.115 × 10⁵ 0.02512 2.293 × 10⁴ 0.63107.964 × 10³ 15.850 8.292 × 10⁴ 0.03981 1.966 × 10⁴ 1.0000 6.752 × 10³25.120 6.322 × 10⁴ 0.06310 1.701 × 10⁴ 1.5850 5.677 × 10³ 39.810 4.920 ×10⁴ 0.10000 1.464 × 10⁴ 2.5120 4.721 × 10³ 63.100 3.956 × 10⁴ 0.158501.265 × 10⁴ 3.9810 3.854 × 10³ 100.000

[0136] Also plotted in FIG. 15 is the tan δ value of the same ElPEpolymer. This value is unitless and is calculated by dividing theviscous modulus value by the elastic modulus. The actual values of tan δand ω utilized in the graph are: tan δ ω tan δ ω tan δ ω 0.5526 0.010001.243 0.2512 1.718 6.310 0.5231 0.01585 1.381 0.3981 1.677 10.000 0.57710.02512 1.543 0.6310 1.620 15.850 0.6597 0.03981 1.615 1.0000 1.55225.120 0.7971 0.06310 1.690 1.5850 1.475 39.810 0.9243 0.10000 1.7292.5120 1.398 63.100 1.080  0.15850 1.737 3.9810 1.315 100.000

[0137] For improved performance in melt blowing applications preferablythe tan δ value is from 0.1 to 3.0 for shear rates between 0.01-100radian/sec.

[0138] A further property of ElPE polymers is illustrated by referenceto FIG. 16. The elastic modulus in dynes/cm², G′, at 0.1 radian/sec.,and 190° C. for several ethylene/1-octene ElPE resins is plotted as afunction of melt index. The resins utilized include those of Examples11, 12, 14-16, 18-22, 24-26, 30 and 31.

[0139] The values of melt index and elastic modulus utilized in thegraph are as follows: Melt Elastic Melt Elastic Melt Elastic IndexModulus Index Modulus Index Modulus 0.10 98760 3.34 4381 18.42 9669 0.1535220 5.34 5858 31.2 4516 0.18 35920 6.38 10480  31.53 5012 0.22 1427010.12 5276 31.69 3238 0.45 11140 10.66 6222 41.02 2972 1.72  3003 16.282697 2.46 10620 16.32 6612

[0140] Typical properties of η* and ω for a conventionally preparedpolyethylene resin are provided in FIG. 17 for comparison purposes.

[0141] It is readily seen that ElPE resins are characterized by highelastic modulus in the melt. In particular, ElPE resins have a meltindex ((I₂), ASTM D-1238 Procedure A, condition E), less than 200,preferably less than 125, most preferably less than 50 and an elasticmodulus greater than 1000 dyne/cm², more preferably greater than 2000dyne/cm². All of the foregoing rheological measurements are performed bystandard techniques such as are disclosed in H. A. Barnes et al.,Introduction to Rheology, Elsevier, publishing, Inc., 1989. Densitiesnormally range from 0.85 to 0.97, preferably from 0.89-0.97. Molecularweight distributions (Mw/Mn) are greater than 2.0, preferably from3.0-10.0. Typically melting points range from 50° C. to 135° C.

[0142] Preferred polymers additionally demonstrate properties ofsubstantially homogeneous polymers as defined in U.S. Pat. No.3,645,992, the teachings of which are herein incorporated in theirentirety by reference thereto. Polymers produced at elevatedpolymerization temperatures, especially temperatures greater than 130°C., may exhibit a heterogeneous melt curve. The polymers of theinvention are further marked by high clarity. In particular the polymershave better optical properties, especially lower haze than typicalethylene polymers, making them especially well suited for film andinjection molding aplications.

[0143] In addition those polymers comprising an olefin and a vinylidenearomatic monomer, especially ethylene and styrene, have surprisinglybeen found to possess elastomeric properties. Thus, such polymers areuniquely suited for use in applications for thermoplastic elastomerssuch as impact modification of thermoplastic and thermosetting polymersincluding bitumens; adhesives; elastomeric moldings; etc.

[0144] The polymers of the invention may be modified by typicalgrafting, crosslinking, hydrogenation, functionalizing, or otherreactions well known to those skilled in the art. With particular regardto the polymers comprising vinylidene aromatic, vinylcyclohexene, or1,4-hexadiene functionality, the same may be readily sulfonated orchlorinated to provide functionalized derivatives according toestablished techniques. Additionally, the vinylcyclohexene basedpolymers are readily crosslinkable by reaction of the unsaturated ringfunctionality.

[0145] The polymers of the present invention, whether or not furthermodified, may be blended with synthetic polymers to provide blendshaving desirable properties. In particular polyethylene,ethylene/a-olefin copolymers, polypropylene, polystyrene,styrene/acrylonitrile copolymers (including rubber modified derivativesthereof), syndiotactic polystyrene, polycarbonate, polyamide, aromaticpolyester, polyisocyanate, polyurethane, polyacrylonitrile, silicone,and polyphenyleneoxide polymers may be blended with the polymericcompositions of the present invention.

[0146] In a highly preferred embodiment of the invention the polymerscontaining ethylene and styrene are elastomeric as defined in thedefinition of an elastomeric substance by ASTM Special TechnicalBulletin No. 184 as a substance that can be stretched at roomtemperature to twice its length and will return to its original lengthupon release.

[0147] In addition to modification of synthetic thermoplastics thepresent polymers are also usefully employed as modifiers for asphalt orbitumen compositions. Desirably the polymers of styrene/ethylene areutilized in this manner.

[0148] The term “bitumen” can generally be defined as mixtures ofhydrocarbons of natural or pyrogenous origin or combinations of both,frequently accompanied by their non-metallic derivatives, which may begaseous, liquid, semi-solid or solid, and which are usually soluble incarbon disulfide. For the purposes of the present invention, bitumen ofa liquid, semi-solid or solid nature may be utilized. From a commercialstandpoint, bitumen is generally restricted to asphalts and tars andpitches. A listing of various bituminous materials which can be utilizedin the present invention include the following:

[0149] I. Asphalts

[0150] 1. Petroleum Asphalts

[0151] A. Straight-reduced asphalts

[0152] 1. Atmospheric or reduced-pressure reduction

[0153] 2. Solvent precipitated, as with propane

[0154] B. Thermal asphalts, as residues from cracking operations onpetroleum stocks

[0155] C. Air-blown asphalts

[0156] 1. Straight-blown

[0157] 2. “Catalytic”-blown

[0158] 2. Native Asphalts

[0159] A. With mineral content below 5 percent

[0160] 1. Asphaltites such as gilsonite, graphamite, and glance pitch

[0161] 2. Bermudez and other natural deposits

[0162] B. With mineral content over 5 percent

[0163] 1. Rock asphalts

[0164] 2. Trinidad and other natural deposits

[0165] II. Tars and Derivatives

[0166] 1. Residua from coke-oven-dried coal tars

[0167] A. Coal tars reduced to float grades, as RT (road tar) grades forpaving purposes

[0168] B. Coal-tar pitches, with reduction carried out tosoftening-point grades

[0169] 2. Residua from other pyrogenous distillates as from water-gas,wood, peat, bone, shale, rosin, and fatty acid tars.

[0170] As can be readily appreciated by those skilled in the art, theweight average molecular weight of the various bitumens can vary over avery wide range, for example such as from about 500 to about 10,000.Additionally, the softening point of the various types of asphalt willalso vary such as from about 50° F. to about 400° F.

[0171] Of the many types of asphalts which may be utilized, petroleum,and native are desired, with petroleum being preferred. Of the petroleumasphalts, the thermal asphalts are preferred.

[0172] The amount of bitumen utilized in the compositions of theinvention may range from about 65 to about 99 parts by weight withpreferred amounts ranging from about 80 to about 98 parts by weight.

[0173] Having described the invention the following examples areprovided as further illustrative and are not to be construed aslimiting. Unless stated to the contrary parts and percentages are basedon weight.

EXAMPLE 1 Preparation of(Tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dichloride

[0174] To 0.443 g (1.90 mmol) ZrCl₄ in a flask was added 8 mL diethylether, then 15 mL tetrahydrofuran (THF). To the resulting slurry wasslowly added a solution of 0.500 g (1.90 mmol) dilithium(tert-butyl-amido)dimethyl(tetramethylcyclopentadienyl)silane in 15 mLTHF. The resulting yellow solution was stirred for several days. Thesolvent was removed to give a gummy residue, which was extracted with5/1 (volume) diethyl ether/pentane and filtered from a white solid. Thesolvent was removed from the yellow filtrate to give a light-yellowpowder. Recrystallization from ether/pentane (5/1) yielded the product(C₅Me₄(Me₂Si—N-tert-Bu)ZrCl₂) as an off-white crystalline solid. Theyield was 0.2207 g (28.2%). Identification was made by ¹³C and ¹H NMR.

[0175] Polymerization

[0176] A. Five mL of a 1.009 M solution of methyl aluminoxane (MAO) intoluene was added to a shot tank containing 25 mL of 4-methyl-1-pentene.The catalyst S solution was prepared by adding 500 μL of a 0.01172 Msolution of C₅Me₄(Me₂SiTert-Bu)ZrCl₂ in toluene to 2 mL of toluene in asecond shot tank. Both shot tanks were sealed, removed from the glovebox, and attached to a 600 mL stainless steel pressure vessel. Thepressure vessel was evacuated and purged with argon.

[0177] The 4-methyl-1-pentene/toluene/MAO solution was added to thepressure vessel and warmed to 89° C. under 620 kPa (90 psig) ethylenewith stirring. Upon addition of the catalyst solution to the4-methyl-1-pentene/MAO/ethylene mixture, the ethylene pressure wasincreased to 1240-1275 kPa (180-185 psig). After 2 hours the solutionwas cooled to 30° C. and vented. The yield of polymer obtained afterdrying under reduced pressure at 100° C. overnight was 10.0 g. ¹³C NMRanalysis of the polymer showed it to be a random copolymer of ethylenewith 4-methyl-1-pentene.

[0178] B. The polymerization procedure of Polymerization A wasessentially repeated except that 50 mL of 1-hexene was used instead of4-methyl-1-pentene and the catalyst concentration was 0.01012 M intoluene. The catalyst solution was added to the 1-hexene/MAO/ethylenemixture and the ethylene pressure was increased to 1240-1275 kPa(180-185 psig). When the catalyst solution was added the temperature ofthe reaction climbed to 139° C. After 30 minutes the solution had cooledto 100° C. Heating and ethylene feed were discontinued and the reactorwas cooled and vented. The yield of polymer obtained after drying underreduced pressure at 100° C. overnight was 36.8 g. ¹³C NMR analysis ofthe polymer showed it to be a random copolymer of ethylene with 1-hexene(8% on a mole basis).

[0179] C. The polymerization procedure of Polymerization A wasessentially repeated except that 213 μL of the catalyst solution(0.01172 M in toluene) was used, and 143 mg of solid MAO was used. Noadditional olefin was added. When the catalyst solution was added to thereactor the temperature increased to 109° C. due to the exothermicpolymerization reaction. The reaction was halted after 1 hour by coolingand venting the reactor. The yield of polyethylene obtained after dryingunder reduced pressure at 100° C. overnight was 11.0 g.

[0180] D. 150 mL of toluene was added to the pressure vessel employed inPolymerization A, followed by 100 g of propylene. A solution of 0.828 gof MAO in 8 mL of toluene was added, followed by 2130 μL of the catalystsolution. The mixture was allowed to react for 3.0 hr at 8° C. Thereaction mixture was quenched with acidic methanol, and 0.38 g of awhite, tacky material was obtained. ¹³C NMR analysis of the polymershowed it to be atactic polypropylene.

EXAMPLE 2 Preparation of(Tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0181] Preparation 1

[0182] (Chloro)(dimethyl)(tetramethylcyclopentadi-2,4-enyl)silane

[0183] To a solution of 21.5 g (167 mmol) dimethyldichlorosilane in 150mL THF cooled to −40° C. was slowly added a solution of 8.00 g (55.6mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 80 mL THF. Thereaction mixture was allowed to warm to room temperature and was stirredovernight. The solvent was removed, the residue was extracted withpentane and filtered. The pentane was removed under reduced pressure togive the product as a light-yellow oil. The yield was 10.50 g (88.0%).¹H NMR (C₆D₆) δ 2.89 (s, 1H), 1.91 (s, 6H), 1.71 (s, 6H), 0.14 (s, 6H);¹³C NMR (C₆D₆) δ 137.8, 131.5, 56.6, 14.6, 11.4, 0.81.

[0184](Tert-butylamino)(dimethyl)(tetramethylcyclopentadi-2,4-enyl)silane

[0185] A solution of 11.07 g (151 mmol) t-butyl amine in 20 mL THF wasadded during 5 minutes to a solution of 13.00 g (60.5 mmol)(chloro)(dimethyl)(tetramethylcyclopentadienyl)silane in 300 mL THF. Aprecipitate formed immediately. The slurry was stirred for 3 days, thenthe solvent was removed, the residue was extracted with pentane andfiltered. The pentane was removed under reduced pressure to give theproduct as a light-yellow oil. The yield was 14.8 g (97.2%). MS: 251 ¹HNMR (C₆D₆) δ 2.76 (S, 1H), 2.01 (s, 6H), 1.84 (s, 6H), 1.09 (s, 9H),0.10 (s, 6H); ¹³C NMR (C₆D₆) δ 135.4, 133.2, 57.0, 49.3, 33.8, 15.0,11.2, 1.3.

[0186] Dilithium(tert-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane

[0187] To a solution of 3.000 g (11.98 mmol)(tert-butylamino)(dimethyl)(tetramethylcyclopentadienyl)-silane in 100mL ether was slowly added 9.21mL of 2.6 M (23.95 mmol) butyl lithium inmixed C₆ alkane solvent. A white precipitate formed and the reactionmixture was stirred overnight, then filtered. The solid was washedseveral times with ether then dried under reduced pressure to give theproduct as a white powder. The yield was 3.134 g (99.8%).

[0188] (Tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride

[0189] 0.721 g (3.80 mmol) Of TiCl₄ was added to 30 mL frozen (−196° C.)THP. The mixture was allowed to warm to −78° C. (dry ice bath). To theresulting yellow solution was slowly added a solution of 1.000 g (3.80mmol) dilithium(tert-butylamido)(dimethyl)tetramethylcyclopentadienyl)silane in 30 mLTHF. The solution was allowed to warm to room temperature while stirringovernight. The solvent was removed from the resulting very darksolution. The residue was extracted with pentane and filtered. Coolingin a freezer caused the separation of a very soluble dark reddish-brownmaterial from a light yellow-green crystalline solid. The solid wasfiltered out and recrystallized from pentane to give the olive-greenproduct. The yield was 0.143 g, 10.2%. ¹H NMR (C₆D₆) δ 2.00 (s, 6H),1.99 (s, 6H), 1.42 (s, 9H)-, 0.43 (s, 6H); ¹³C NMR (C₆D₆) δ 140.6,137.9, 104.0, 62.1, 32.7, 16.1, 13.0, 5.4.

[0190] Preparation 2

[0191] In a drybox, 4.0 mL of 2.0 M isopropylmagnesium chloride indiethyl ether was syringed into a 100 mL flask. The ether was removedunder reduced pressure to leave a colorless oil. 20 mL of a 4:1 (byvolume) toluene:THF mixture was added followed by 0.97 g of(tertbutylamino)dimethyl(tetramethylcyclopentadienyl)silane. Thesolution was heated to reflux. After 8-10 hours, a white precipitatebegan to form. After refluxing for a total of 27 hours, the solution wascooled and the volatile materials were removed under reduced pressure.The white solid residue was slurried in pentane and filtered to leave awhite powder (1.23 g, 62% yield) of Me₄C₅SiMe₂N-t-BuMg₂Cl₂(THF)₂.

[0192] In the drybox, 0.50 q of TiCl₃(THF)₃ was suspended in 10 mL ofTHF. 0.69 g of solid Me₄C₅SiMe₂N-t-BuMg₂Cl₂(THF)₂ was added, resultingin a color change from pale blue to deep purple. After 15 minutes, 0.35g of AgCl was added to the solution. The color immediately began tolighten to a pale green-yellow. After 1½ hours, the THF was removedunder reduced pressure to leave a yellow-green solid. Toluene (20 mL)was added, the solution was filtered, and the toluene was removed underpressure to leave a yellow-green microcrystalline solid, 0.51 g(quantitative yield) The product's identity was confirmed as(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride by ¹H NMR, (C₆D₆): δ 1.992 (s), 1.986 (s), 1.414 (s), 0.414(s).

[0193] Preparation 3

[0194] TiCl₄, 0.72 g (3.80 mmol) was added to 35 mL of frozen THF (−196°C.) in a flask. The mixture was warmed to −78° C. A solution of 1.0 g(3.80 mmol) dilithium(tert-butylamido)dimethyl(tetramethylcyclopentadienyl)-silane in THF wasslowly added. The resulting yellow solution was warmed to roomtemperature and stirred overnight. The solvent was removed to give adark residue which was extracted with pentane and filtered. The product(C₅Me₄(Me₂SiN-t-Bu)TiCl₂) was obtained as a dark greenish-yellowcrystalline material after being recrystallized twice from pentane at−35 to −40° C. Identification was confirmed by ¹³C and ¹H NMR.

[0195] Preparation 4

[0196] In the drybox, TiCl₃(THF)₃ (2.0 g, 5.40 mmol) was suspended in 40mL of THF. Dilithio(tert-butylamido)dimethyl(tetramethylcyclopentadienyl)silane (1.42 g,5.39 mmol) was then added, resulting in an immediate darkening of thecolor, eventually to a deep blue. After 1½ hours of stirring, AgCl (0.84g, 5.86 mmol) was added. The color immediately began to lighten to ared/orange. After 1½ hours of stirring, the THF was removed underreduced pressure. Diethyl ether (50 mL) was added, the solution wasfiltered, and the volatile materials were removed under reducedpressure. This yielded 1.91 g of the product(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)-silanetitaniumdichloride. ¹H NMR (C₆D₆): δ 1.992 (s), 1.987 (s), 1.415 (s), 0.415 (s).

[0197] Polymerization

[0198] Polymerization of a styrene/ethylene mixture was accomplished bycombining 1.65 mL of a 10% solution of MAO in toluene with a solution of45 mL of toluene and 50 mL styrene in a stainless steel shot tank. 250μL of a 0.010 M solution of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride was added to 2.5 mL of toluene in a second shot tank. Bothshot tanks were sealed, removed from the glove box, and attached to a600 mL stainless steel pressure vessel. The pressure vessel wasevacuated and purged with argon.

[0199] The styrene/toluene/MAO solution was added to the pressure vesseland warmed to 89° C. under 620 kPa (90 psig) ethylene with stirring. Atthis time the catalyst solution was added and the pressure was increasedto 1275 kPa (185 psig) and regulated between 1240-1275 Kpa (180-185psig). An exotherm raised the temperature to 95° C. The temperature waslowered to 90° C. and was then regulated between 90-92° C. for theremainder of the reaction.

[0200] After 1.0 hr. the ethylene feed was discontinued. The reactionwas vented to the atmosphere and cooled to 30° C. at which time methanolwas added. The product was collected, washed with methanol and residualsolvents were removed under reduced pressure at 120° C. which resultedin 9.02 g of material. ¹³C NMR analysis of this material showed it to bea random copolymer of styrene (15.2% on a molar basis) and ethylene,free of peaks attributed to polystyrene.

EXAMPLE 3 Olefin Polymerization

[0201] Ethylene was polymerized by combining 5 mL of a 1 M solution oftriethyl aluminum in mixed C₆ alkane solvent and 0.5 mL of a 0.01 Msolution of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride in toluene in a stainless steel (SS) shot tank. The titaniumcatalyst and triethyl aluminum cocatalyst solution was then added underpressure to a 3 L SS pressure vessel containing 2 L of mixed alkanesolvent (Isopar E, available from Exxon Chemicals, Inc.) under 3100 kPa(450 psig) ethylene at 150° C. The reaction temperature was maintainedat 150° C. for 10 minutes. The ethylene pressure was held constant, anda mass-flow meter measured the uptake of ethylene to be 15.7 g. Thepolymer solution was then removed from the pressure vessel and thepolyethylene was recovered after drying under reduced pressure at 90° C.overnight. Yield was 15.7 g.

EXAMPLE 4 Olefin Copolymer Polymerization

[0202] In a glove box under argon atmosphere, 5.0 mL of 1.0 M solutionof methylaluminoxane (MAO) in toluene was combined with 50 mL of1-octene in a stainless steel (SS) shot tank fitted with ball valves onboth ends. In another SS shot tank 500 μL (5.06 mmol) of a 0.0101 Msolution of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdichloride in toluene was added to 2 mL toluene.

[0203] The shot tanks were sealed, removed from the glove box andattached to a 600 mL SS pressure vessel. The pressure vessel wasevacuated and purged with argon. The solution of 1-octene and MAO wasadded to the pressure vessel. The solution was warmed to 89° C. under620 kPa (90 psig) ethylene with stirring. At this time the catalystsolution was added. An exothermic reaction occurred which raised thetemperature to 142° C. The ethylene pressure was maintained between1327-1362 kPa (190-195 psig).

[0204] After 0.5 hour the ethylene feed was discontinued. The reactorwas cooled to 30° C., vented to the atmosphere, and the reaction wasquenched with methanol. The product was collected on a fritted filterand washed with methanol. Residual solvents were removed under reducedpressure at 110° C. which resulted in 35 g of material. ¹³C NMR analysisindicated that 1-octene was incorporated into the polymer in an amountof 7.8 mole percent. Differential Scanning Calorimetry (DSC) indicated aTm of 100° C. Density 0.895 g/mL, Mw=44,000, Mw/Mn=6.8

EXAMPLE 5 Olefin Copolymer Polymerization

[0205] The procedure of Example 4 was substantially repeated exceptingthat 50 mL of 1-hexene was used instead of 1-octene. The temperature ofthe reaction was maintained at 133-140° C. Polymer yield was 37 g.Incorporation of 1-hexene was 8 percent on a molar basis, 21% by weight.

EXAMPLE 6 α-Olefin Homopolymerization

[0206] A. 4-Methyl-1-pentene (6.0 mL, 4.0 g) was added to 1.0 mL of a1.0 M MAO solution in toluene in a 20 mL crimp-top vial. To this wasadded 100 μL of a 0.01172 M toluene solution of the zirconium complexcatalyst of Example 4. The vial was sealed, shaken, and allowed to standat room temperature (ca. 20° C.) for 16 hours, then heated to 48° C. foran additional 24 hours. The viscous polymer solution was precipitated bythe addition of methanol. The resulting polymer was collected and thevolatile components removed under reduced pressure for four hours at100° C. to give 3.8 g of a clear polymer (95 percent yield). ¹³C NMRanalysis indicated that the polymer was atactic poly-4-methyl-1-pentene.

[0207] B. The procedure of Polymerization A was essentially repeated.3.4 g of 1-hexene, 1.0 mL of MAO solution, and 100 μL of the catalystsolution were added to a 20 mL crimp-top vial in an argon-filled drybox.The vial was sealed and heated at 50° C. overnight. After quenching withacidified ethanol and drying there was obtained 3.0 g of poly(1-hexene).

EXAMPLE 7 Ethylene Homopolymerization

[0208] A SS shot tank was charged with 500μL (5.0 μmol) of a 0.010 Mtoluene solution of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride and 2.5 mL of toluene in an argon filled glove box. In asecond SS shot tank, 5.0 mL of a 1.0 M solution of MAO in toluene wasadded to 92 mL of toluene. Both shot tanks were sealed, removed from theglove box and attached to a 600 mL pressure vessel. The pressure vesselwas evacuated and flushed with argon and then flushed with ethylene. Thecocatalyst solution was added to the pressure vessel and heated to 89°C. under an ethylene pressure of 620 kPa (90 psig). The catalystsolution was added to the reactor at this time. The temperature rose to109° C. within seconds as a result of an exothermic reaction. Theethylene pressure was regulated between 1241-1275 kPa (180-185 psig).After about 0.5 hours the reactor temperature had increased to about110° C. and the uptake of ethylene increased. After 1.0 hours ethylenefeed was discontinued, the reactor was vented to the atmosphere, andallowed to cool. The pressure vessel was opened, quenched with methanol,and the polymer was isolated. After removing the volatile components,the yield of polyethylene was 24 g.

EXAMPLE 8 Hindered Vinyl Aliphatic Monomer Polymerization

[0209] 4-vinylcyclohexene was purified by vacuum distillation from Na/Kalloy. In a glove box, 50 mL of 4-vinylcyclohexene was combined with 5.0mL of a solution of 1.0 M methylaluminoxane (MAO) cocatalyst in toluenein a stainless steel (SS) shot tank fitted with ball valves on bothends. 500 μL of a 0.010 M solution of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdichloride in toluene was added to 2 mL toluene in a similarly fitted SSshot tank.

[0210] The shot tanks were sealed, removed from the glove box andattached to a 600 mL SS pressure vessel. The pressure vessel wasevacuated and purged with argon. The solution of 4-vinylcyclohexene andMAO was added to the pressure vessel. The solution was warmed to 89° C.under 620 kPa (90 psig) ethylene with stirring. At this time thecatalyst solution was added. An exothermic reaction occurred whichraised the temperature to 114° C. The ethylene pressure was maintainedbetween 1327-1362 kPa (190-195 psig).

[0211] After 1 hour the ethylene feed was discontinued. The reactor wascooled to 30° C., vented to the atmosphere, and the reaction wasquenched with acidified methanol. The product was collected on a frittedfilter and washed with methanol. Residual solvents were removed underreduced pressure at 110° C. which resulted in 12.6 g of material. ¹³CNMR analysis indicated that vinylcyclohexene was incorporated into thepolymer in an amount of about 1.5 mole percent.

EXAMPLE 9 Ethylene/Styrene Copolymerization

[0212] The above polymerization procedure was substantially followedexcept that the reaction temperature was 90° C. The reactor was filledwith 150 mL of mixed alkane solvent, 500 mL of styrene and 8 mL of 15percent MAO in toluene (1000 Al:Ti). The reactor was saturated with 180psig of ethylene, and 20 micromoles of [(C₅Me₄)SiMe₂(N-phenyl)]TiCl₂ wasadded to begin the polymerization. Ethylene was provided on demand at3102 kPa (450 psig). After 60 minutes, the solution was drained from thereactor into a container which had a small amount of antioxidant. Thepolymer was dried under vacuum. The polymer yield was 26.6 g, melt index(I₂)=26.6. ¹³C NMR NMR analysis indicated the polymer was 47 molepercent styrene (76 weight percent). No isotactic, atactic, orsyndiotactic sequences were observed.

EXAMPLE 10 Ethylene/Styrene Copolymerization

[0213] The reaction conditions of Example 9 are substantially repeatedto prepare styrene/ethylene copolymers having differing styrene content.The catalyst was(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride except where noted. MAO cocatalyst was employed in an amountto provide an Al:M atomic ratio of 1000:1. Reaction conditions arecontained in Table I. TABLE I mg T Solvent Ethylene Styrene Time Yieldmol % Run (complex) (° C.) (mL)^(b) Pressure (mL) hr. (g) Styrene MwMw/Mn 1 0.92 90 T,50 1241 50 1.0 9 15.2 147,000 2.5 2 2.50 90 T,138 ″138 2.0 29 18.4 65,100 2.7 3 2.20 90 T,160 ″ 80 2.0 27 11.7 70,100 2.6 42.20 90 T,204 ″ 36 2.0 30 8.1 72,300 2.5 5 3.70 90 I,350 1517 350 1.0 5710.3 121,000 2.8 6 3.70 90 I,525 ″ 175 0.75 70 6.8 304,000 2.6 7 3.70 90I,600 ″ 100 0.33 46 4.8 180,000 2.6 8 3.70 90 I,440 ″ 260 0.33 43 9.0172,000 2.5 9 1.90 90 I,650 ″ 50 0.5 12 2.5 113,000 3.2 10 1.90 90 I,650″ 50 0.5 40 2.8 154,000 2.6 11 2.20 90 T,180 1241 60 2.0 30 13.3 78,6003.1 12^(a) 2.30 90 T,180 ″ 60 2.0 11 37.0 — —

EXAMPLES 11-32

[0214] In these examples, a 4 liter autoclave was charged with 2000 mLof mixed alkane solvent followed by various amounts of 1-octene. Thecatalyst was(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride, dissolved in toluene. The cocatalyst was a 10% solution ofMAO in toluene. Hydrogen, if desired, was added by expansion from a 100mL vessel at a pressure indicated above the operating pressure of thereactor. The reactor was filled with solvent, 1-octene and MAO, heatedto the reaction temperature, then pressurized to 3102 kPa (450 psig)with ethylene until the solution was saturated. The hydrogen (if any)was expanded into the reactor, followed by the addition of the catalystsolution. After 10 minutes, the solution was drained from the reactorinto a container which had a small amount of antioxidant (Irganox 1010®,available from Ciba-Geigy). The polymer was dried under vacuum. Resultsare contained in Table II. TABLE II Reactor Polymer Temp Octene ΔH₂Catalyst Yield Melt Density Melt Example (° C.) (mL) (kPa)^(a) mmolesAl:Ti^(b) (g) Mw Mn Mw/Mn Point ° C. g/mL Index^(c) 11 140 300 0 0.02500:1 182 — — —  91 0.9063 1.72 12 160 300 0 0.02 ″ 61 50,900 12,8003.98 95^(d) 0.9177 16.28 13 140 300 689 0.02 ″ 157 57,500 14,900 3.86 96 0.9175 7.91 14 160 300 ″ 0.02 ″ 58 38,500 10,700 3.60 100^(d) 0.923031.69 15 140 150 345 0.02 ″ 128 66,500 17,400 3.82 105 0.9174 3.34 16160 150 ″ 0.02 ″ 90 53,000 13,400 3.96 106^(d) 0.9317 10.66 17 140 450 ″0.02 ″ 148 71,700 17,100 4.19  86 0.9010 3.84 18 160 450 ″ 0.02 ″ 5542,500 11,400 3.73 90^(d) 0.9045 31.20 19 150 150 0 0.02 ″ 75 71,70016,500 4.35 108 0.9276 2.46 20 150 150 689 0.02 ″ 85 44,900 13,400 3.35108 0.9261 18.42 21 150 450 0 0.02 ″ 107 62,500 14,800 4.22 92^(d)0.9090 5.34 22 150 450 689 0.02 ″ 85 58,200 12,900 4.51 124 0.9516 6.3823 150 300 345 0.02 ″ 100 51,000 14,000 3.64 95^(d) 0.9130 13.62 24 150300 ″ 0.02 ″ 93 53,700 14,700 3.65 96^(d) 0.9121 10.12 25 150 300 6890.02 ″ 115 43,000 14,200 3.03 95^(d) 0.9118 31.53 26 130 150 345 0.02 ″166 105,000 23,200 4.53 109 0.9198 0.18 27 130 150 ″ 0.02 250:1 147136,000 29,400 4.63 110 0.9197 0.15 28 130 150 ″ 0.02 100:1 83 146,00026,300 5.55 105 0.9153 0.15 29 110 150 ″ 0.01 250:1 98 161,000 42,0003.83 106 0.9140 0.15 30 120 300 ″ 0.02 ″ 123 112,000 28,500 3.93  890.9016 0.45 31 110 450 ″ 0.02 ″ 145 130,000 37,400 3.48  76 0.9000 0.2232 110 300 ″ 0.02 ″ 160 141,000 35,600 3.96  82 0.9000 0.15

EXAMPLES 33-42

[0215] The procedure of examples 11-32 was substantially repeated,except that the catalyst was(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdichloride. Results are contained in Table III. TABLE III Example Temp °C. mL Octene ΔH₂ (kPa) Zr (mmole) Al:Zr^(a) Zr eff × 10^(−3b) 33 150 300345 0.02 500 50 34 140 300 ″ 0.01 500 122 35 130 300 ″ 0.005 500 285 36130 450 ″ 0.005 500 302 37 130 150 ″ 0.005 500 230 38 130 150 ″ 0.01 250158 39 130 150 ″ 0.02 100 104 40 130 300 ″ 0.01 100 154 41 140 450  00.015 200 84 42 140 450 689 0.02 200 101

EXAMPLES 43-57

[0216] The procedure of Examples 11-32 was substantially followed exceptthat a 2000 mL reactor was used. The catalyst was(tert-butylamido)dimethyl-(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride (2 mL of a 0.005 M solution in toluene, 10 μmoles). Thecocatalyst was 15% MAO in toluene (2 mL, 500 Al:Ti). Results arecontained in Table IV. TABLE IV Ex- am- Temp. ΔH₂ 1-Octene Melt ple ° C.(kPa)^(a) mole percent g Polymer Index^(b) Density 43 100 172 1.59 70.0<.1 0.8700 44 80 ″ 1.59 67.0 <.1 0.8672 45 90 ″ 1.85 98.2 0.8582 46 100″ 2.12 118.3 0.96 0.8575 47 100 345 1.85 131.9 7.48 0.8552 48 80 1722.12 139.3 0.93 0.8528 49 90  0 1.59 104.4 0.25 0.8594 50 90 345 2.12133.1 0.8556 51 90 172 1.85 130.2 0.8550 52 100  0 1.85 110.0 0.660.8570 53 90 172 1.85 141.0 0.8545 54 80 345 1.85 161.2 5.44 0.8525 5580  0 1.85 118.1 0.48 0.8536 56 90  0 2.12 150.8 3.12 0.8516 57 90 3451.59 136.7 3.43 0.8578

EXAMPLES 58-77 Olefin Polymerization

[0217] Ethylene and/or ethylene/1-octene were respectively polymerizedas a homopolymer or copolymer by adding a solution of the appropriatecatalyst in combination with MAO or triethyl aluminum cocatalyst to a 3LSS pressure vessel containing mixed C₆ alkane solvent/1-octene (withvarying ratios) under 3100 kPa (450 psig) of ethylene at 150° C. (or175° C. where indicated) for 10 minutes. The ethylene pressure was heldconstant and a mass flow meter measured the uptake of ethylene. Theconsequent polymer was then removed from the pressure vessel and driedunder reduced pressure at 90° C. overnight. Results are contained inTable V. TABLE V Example Catalyst^(a,b) Solvent/Octene^(c) Wt. ofpolymer (g) Melt Index (I₂) Mw Mn Mw/Mn 58 Ti 1/1 61.1 79.0 45,600 91005.01 59 Ti 2/0.3 48.7 1.7 88,300 10100 8.74 60 Ti 1/1 41.5 137.6 36,3009950 3.68 61 Zr 1/1 55.2 1324.9 — — — 62 Zr 2/0.15 33.3 10.3 — — — 63 Zr2/0 25.8 8.8 58,400 5310 10.90 64 Zr 0/2 102.9 168.1 30,900 8150 3.79 65^(d) Zr 2/0 17.8 147.1 — — — 66 Zr 2/0 25.3 240.8 — — — 67 Ti 2/015.6 4.4 — — — 68 Zr 2/0 20.6 2.8 101,000 7700 13.10 69 Zr 2/0.3 44.017.1 47,300 6550 7.22 70 Zr 0/2 96.6 149.2 43,500 4710 5.87 71 Ti 1/147.5 25.8 54,000 10800 5.00 72 Ti 2/0.3 74.5 56.3 44,400 12100 3.67 73Ti 2/0.3 75.0 56.9 44,700 9800 4.56 74 Ti 2/0 15.6 — — — —  75^(e) Ti2/0.15 19.9 — — — — 76 Ti 2/0.15 34.5 1.0 — — — 77 Zr 0/2 88.3 111.735,100 6440 5.45

EXAMPLE 78 Preparation of Supported(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0218] 0.100 g of dehydroxylated silica (—OH concentration≈1 mmol/gSiO₂) was slurried in 20 mL of mixed C₆ alkane solvent under a nitrogenatmosphere in a dri-box, with stirring in a 50 mL Erlenmeyer flask. Fromthis slurry 1.0 mL was removed by syringe and combined with 1.10 mL of a0.011 M toluene solution of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride in a 5 mL rounded-bottomed flask and stirred for 12 h. Afterthis period 6.7 mL of a 10 percent (w/w) solution of methyl aluminoxane(MAO) in toluene was added to the silica containing solution.

[0219] Polymerization

[0220] The polymerization was conducted by adding under pressure theabove titanium/silica/MAO slurry in a 3 L SS pressure vessel containing2 L of mixed alkane solvent under 3100 kPa (450 psig) of ethylene at150° C. for 10 minutes. The ethylene pressure was held constant and amass flow meter measured the uptake of ethylene to be 26.7 g. Thepolymer solution was then removed from the pressure vessel and thepolyethylene was recovered after drying under reduced pressure at 90° C.overnight. Yield was 30.0 g.

EXAMPLE 79 Preparation of(2-Methoxyphenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0221] ((Tetramethylcyclopentadienyl)dimethylsilyl)(2-methoxyphenyl)amine

[0222] To 1.3 g (5.9 mmol)((tetramethylcyclopentadienyl)dimethylsilyl)chloride in 50 mLtetrahydrofuran (THF) was added 0.86 g (5.9 mmol) sodium2-methoxyanilide. The mixture was stirred overnight. The solvent wasremoved under reduced pressure and the residue extracted with pentane.The pentane extracts were filtered, combined, and concentrated to give apale yellow liquid. Yield 1.4 g (79%). ¹H NMR (benzene-d₆) _(—)6.91 (m,2.2), 6.74 (m, 1.1), 6.57 (d, 1.1, J=9), 4.25 (s, 1), 3.32 (s, 3.7),1.93 (s,6.7), 1.80 (s, 6.8), 0.13 (s, 6.3).

[0223] Dilithium((tetramethylcyclopentadienyl)dimethylsilyl)(2-methoxyphenyl)amide.

[0224] To 1.4 g (4.6 mmol) ((tetramethylcyclopentadienyl)dimethylsilyl)(2-methoxyphenyl)amine in diethyl ether was added dropwise 3.9 mL of 2.5M butyl lithium (9.8 mmol) in hexane solvent. A white precipitateformed. Pentane was added to the mixture. The slurry was filtered andthe solids washed with pentane.

[0225](2-Methoxyphenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0226] To 1.6 g of dilithium((tetramethylcyclopentadienyl)dimethylsilyl) (2-methoxyphenyl)amideslurried in toluene was added 0.85 g TiCl₄. The mixture was stirred forthree days, filtered, and the solvent was removed under reducedpressure. The residue was slurried in pentane and filtered to give adark powder. Yield 0.77 g (41%). ¹H NMR (benzene-d₆) δ 4.10 (s, 3), 2.20(s, 6.4), 1.99 (s, 6.6), 0.40 (s, 6.3).

EXAMPLE 80 Preparation of (4-Fluorophenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride

[0227] ((Tetramethylcyclopentadienyl)dimethylsilyl)(4-fluorophenyl)amine

[0228] Equimolar quantities of((tetramethylcyclopentadienyl)dimethylsilyl)chloride and lithium4-fluoro anilide were combined in THF and the mixture stirred overnight.The solvent was removed under reduced pressure. ¹H NMR (benzene-d₆) δ6.79 (m, 2.5), 6.33 (m, 2.4), 2.95 (s,1), 2.90 (s, 1), 1.87 (s, 6.9),1.79 (s, 6.9), 0.02 (s, 5.8).

[0229] Dilithium ((tetramethylcyclopentadienyl)dimethylsilyl)(4-fluorophenyl)amide

[0230] ((Tetramethylcyclopentadienyl)dimethylsilyl)(4-fluorophenyl)amine in diethyl ether solvent and butyl lithium 2.5 Min hexane solvent were combined in equivalent amounts. A whiteprecipitate formed. Pentane was added to the slurry. The precipitate wasfiltered, washed with pentane and dried. ¹H NMR (THF-d₈) δ 7.28 (m,2.0), 6.77 (m, 2), 3.27 (s, 2.7), 2.05 (s, 5.2), 2.01(s, 5.2), 0.44 (S,4.6)

[0231](4-Fluorophenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride

[0232] To 0.59 g (1.6 mmol) TiCl₃-3THF in 50 mL THF was added 0.50 g(1.7 mmol) dilithium((tetramethylcyclopentadienyl)dimethylsilyl)(4-fluorophenyl)amide. After0.5 hr, 0.25 g (1.8 mmol) AgCl was added. After 2 hr the solvent wasremoved under reduced pressure. The residue was extracted with diethylether. The ether extracts were filtered, combined, and concentratedunder reduced pressure to give a red glassy solid. Dissolution intotoluene and reconcentration produced a waxy solid. This solid wasextracted into pentane. The pentane extracts were filtered, combined,and concentrated to produce a waxy solid. This was slurried with a smallamount of pentane (2 mL) and filtered to give a red powder. The yieldwas 0.18 g (28%). ¹H NMR (benzene-d₆) δ 7.10 (t), 6.80 (t), 2.00 (s),1.97 (s), 0.35(s).

[0233] Polymerization

[0234] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 450psig of ethylene, and a 75 mL tank of hydrogen was pressurized to 500psig to give a delta pressure of 50 psi. The hydrogen was expanded intothe reactor, and 10 micromoles of the above complex was added to beginthe polymerization. Ethylene was provided on demand at 450 psig. After10 minutes, the solution was drained from the reactor into a containerwhich had a small amount of antioxidant. The polymer was dried undervacuum. The polymer yield was 12.8 g, Mw=103,000, Mw/Mn=4.77,density=0.9387, melt index=6.37.

EXAMPLE 81 Preparation of((2,6-Di(1-methylethyl)phenyl)amido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0235] Dilithium((tetramethylcyclopentadienyl)dimethylsilyl)(2,6-di(1-methylethyl)phenyl)amidewas prepared in a manner analogous to Example 80.

[0236] To 1.5 g (4 mmol) TiCl₃-3THF in 25 mL THF was added 1.5 g (4mmol) dilithium((tetramethylcyclopentadienyl)dimethylsilyl)(2,6-di(1-methylethyl)phenyl)amide.After 0.5 hr 0.63 g (4 mmol) AgCl was added. After 1.5 hr the solventwas removed under reduced pressure. The residue was extracted withpentane (3×8 mL). The pentane insoluble residue was extracted withdiethyl ether. The ether extract was filtered and evaporated to drynessto give a yellow crystalline solid. ¹H NMR (benzene-d6) d 3.04 (heptet,2, J=6.7), 2.18 (s, 5.8), 1.98 (s, 5.8), 1.49 (d, 5.8, J=6.5), 1.12 (d,6.2, J=6.8), 0.48 (s, 5.2).

[0237] Polymerization

[0238] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 450psig of ethylene, and a 75 mL tank of hydrogen was pressurized to 500psig to give a delta pressure of 50 psi. The hydrogen was expanded intothe reactor, and 10 micromoles of the above complex was added to beginthe polymerization. Ethylene was provided on demand at 450 psig. After10 minutes, the solution was drained from the reactor into a containerwhich had a small amount of antioxidant. The polymer was dried undervacuum. The polymer yield was 14.7 g.

EXAMPLE 82 Preparation of(4-Methoxyphenylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0239] To 0.73 g TiCl₄-2THF in 30 mL toluene was added 0.7 g ofdilithium ((tetramethylcyclopentadienyl)dimethylsilyl)(4-methoxyphenyl)amide (prepared in a method analogous toExample 81. The mixture was stirred for two days, filtered, andconcentrated under reduced pressure. The residue was slurried in pentaneand filtered to give a brick red powder. Yield 0.61 g (67%). ¹H NMR(benzene-d₆) δ 7.28 (d, 2, J=8.8), 6.78 (d, 2, J=8.9), 3.27 (s, 2.8),2.05 (s, 5.6), 2.01 (s, 5.6), 0.44 (s, 4.8).

[0240] Polymerization

[0241] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 450psig of ethylene, and a 75 mL tank of hydrogen was pressurized to 500psig to give a delta pressure of 50 psi. The hydrogen was expanded intothe reactor, and 10 micromoles of the above complex was added to beginthe polymerization. Ethylene was provided on demand at 450 psig. After10 minutes, the solution was drained from the reactor into a containerwhich had a small amount of antioxidant. The polymer was dried undervacuum. The polymer yield was 7.2 g, Mw=79,800, Mw/Mn=21.5, meltindex=2.90.

EXAMPLE 83 Preparation of(tetramethyl-η⁵-cyclopentadienyl)dimethyl(1-methylethoxy)silanetitaniumtrichloride

[0242] (Tetramethylcyclopentadienyl)dimethyl(1-methylethoxy)silane

[0243] To 1.0 g (4.8 mmol)(tetramethylcyclopentadiene)dimethylsilylchloride in 10 mL toluene wasadded 0.38 mL (5.0 mmol) 2-propanol followed by 0.66 mL (4.7 mmol)triethylamine. The mixture was filtered and the solids washed with mixedC₆ alkane solvent. The wash and the filtrate were combined andconcentrated under reduced pressure to give a pale yellow liquid. ¹H NMR(benzene-d₆) 63.85 (heptet, 1, J=6.0), 2.9 (s, 1.1), 2.03 (s, 5.7), 1.8(s, 6.3), 1.10 (d, 6.3, J=6.0), −0.02 (s, 5.0).

[0244] Potassium(dimethyl(1-methylethoxy)silyl)tetramethylcyclopentadienide)

[0245] To 0.51 g (2.1 mmol) (tetramethylcyclopentadienyl)dimethyl(1-methylethoxy)silane in toluene was added 0.33 g (2.5 mmol) potassiumbenzide. The solution was filtered after 3 days and the solvent wasremoved under reduced pressure to give an oil. The oil was washed withpentane. Residual pentane was removed under reduced pressure to give anorange glassy solid. ¹H NMR (THF-d₈) δ 3.89 (heptet, 1, J=6.1), 2.00(s,6.1), 1.87 (s, 5.7), 1.05 (d, 5.1, J=6.1), 0.22 (s, 4.4).

[0246](Tetramethyl-η⁵-cyclopentadienyl)dimethyl(1-methylethoxy)silanetitaniumtrichloride

[0247] To 0.42 g (1.1 mmol) TiCl₃.3THF in 50 mL THF was added dropwise0.83 mmol potassium(dimethyl(1-methylethoxy)silyl)tetramethylcyclopentadienide) in 15 mLTHF. One hour after addition was complete 0.2 g (1.3 mmol) AgCl wasadded. The resulting mixture was stirred for 18 hr. The solvent wasremoved under reduced pressure and the residue extracted with pentane.The pentane extracts were filtered, combined, and evaporated to a redoil. The red oil was slurried in pentane and the mixture was filtered.The filtrate was stored art −30° C. for 3 weeks which resulted in theprecipitation of an orange solid. The solution was decanted from thesolid. ¹H NMR (benzene-d₆) δ 3.8(heptet, 1, J=6.0), 2.35 (s, 6.9), 1.86(s, 7.4), 1.04 (d, 7.1, J=6.0), 0.45(s, 6.7).00(s), 1.97 (s), 0.35 (s).

EXAMPLE 84 Preparation of1-(Tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)-1,1,2,2-tetramethyldisilanetitaniumdichloride

[0248]1-Chloro-2-(tetramethylcyclopentadienyl)-1,1,2,2-tetramethyldisilane

[0249] To a solution of 4.802 g (25.7 mmol)1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether wasslowly added a solution of 2.285 g (12.8 mmol) sodium1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. Thereaction mixture was stirred several hours, then the solvent wasremoved, the residue was extracted with pentane and filtered. Thepentane was removed under reduced pressure to give the product as alight-yellow oil. Mass spec: m/e 272 (8%). ¹H NMR (C₆D₆) δ 2.70 (s, 1H),1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); ¹³C NMR (C₆D₆) δ135.8, 134.0, 54.4, 14.6, 11.4, 3.2, −2.4.

[0250]1-(Tert-butylamino)-2-(tetramethylcyclopentadienyl)-1,1,2,2-tetramethyldisilane

[0251] To a solution of 3.000 g (11.0 mmol)1-chloro-2-(tetramethylcyclopentadienyl)-1,1,2,2-tetramethyldisilane in50 mL ether was added 2.422 g (33.1 mmol) tertbutylamine. Precipitateformed rapidly. The slurry was stirred for several days at roomtemperature, then was gently heated to drive the reaction to completion.The solvent was removed, the residue was extracted with pentane, theamine hydrochloride was filtered and the pentane was removed underreduced pressure to give the product as a yellow oil. The yield was3.150 (92.5%). Mass spec: m/e 309. ¹H NMR (C₆D₆) δ 2.75 (s, 1H), 1.95(s, 6H), 1.82 (s, 6H),1.08 (s, 9H), 0.51 (s, 1H), 0.24 (s, 6H), 0.16 (s,6H); ¹³C NMR (C₆D₆) δ 135.2, 134.4, 55.2, 50.3, 34.1, 14.9 11.6, 3.3,−1.4.

[0252] Dilithium1-(tert-butylamido)-2-(tetramethylcyclopentadienyl)-1,1,2,2-tetramethyldisilane

[0253] To a solution of 3.00 g (9.72 mmol)1-(tert-butylamino)-2-(tetramethylcyclopentadienyl)-1,1,2,2-tetramethyldisilanein 100 mL ether was slowly added 7.70 mL of 2.60 M (20.2 mmol) butyllithium in mixed C₆ alkane solvent. The resulting slurry was stirredseveral hours, then filtered and washed with ether, then dried underreduced pressure to give the product as a white powder. The yield was2.918 g (93.4%). ¹H NMR (THF d-8) δ 2.05 (s, 6H), 1.91 (s, 6H),0.87 (s,9H), 0.25 (s, 6H), −0.03 (s, 6H); ¹³C NMR (THF d-8) δ 117.3, 113.6,53.5, 38.4, 34.1, 14.2 11.3, 8.4, 2.2.

[0254] 1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopenta-dienyl)-1,1,2,2-tetramethyldisilane titanium dichloride

[0255] A slurry of 0.7500 g (2.333 mmol)dilithium1-(tert-butylamido)-2-(tetramethylcyclopentadienyl)-1,1,2,2-tetramethyldisilane and 0.7790 g (2.333 mmol) TiCl₄(THF)₂ in 50mL toluene was stirred for several days. The red-orange reaction mixturewas filtered and the solvent was removed to give a sticky red solid.This was extracted with pentane and filtered. After concentration andcooling at −35° C. in a freezer, the shiny microcrystalline red productwas collected on a frit and washed with cold pentane to remove a darkred oily material. Yield: 0.3643 g, 36.6%. ¹H NMR (C₆D₆) δ 2.20 (s, 6H),1.94 (s, 6H), 1.48 (s 9H), 0.44 (s, 6H), 0.43 (s, 6H). ¹³C NMR(C₆D₆) δ137.7, 135.5, 112.7, 65.9, 35.4, 16.6, 12.5, 2.8, −2.1.

[0256] Polymerization

[0257] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 3102kPa (450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurizedto 3447 kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was12.1 g, Mw=62,400, Mw/Mn=8.45, melt index=6.14, density=0.9441.

EXAMPLE 85 Preparation of1-(Tert-butylamido)-2-(tetramethyl-η⁵-cyclopenta-dienyl)-1,1,2,2-tetramethyldisilanezirconium dichloride

[0258] A slurry of 0.7500 g (2.333 mmol) dilithium1-(tertbutylamido)-2-(tetramethylcyclopentadienyl)-1,1,2,2-tetramethyl-disilane(prepared according to the technique of Example 84) and 0.5436 g (2.333mmol) ZrCl₄ in 75 mL toluene was stirred for several days. The paleyellow reaction mixture was filtered and the solvent was removed. Theresidue was extracted with pentane and filtered. After concentration andcooling at −35° C. in a freezer, the product as colorless crystals wascollected on a frit. Yield: 0.6720 g, 61.3%. ¹H NMR (C₆D₆) δ 2.14 (s,6H), 1.94 (s, 6H), 1.49 (s, 9H), 0.36 (s, 6H), 0.34 (s, 6H) ¹³C NMR(C₆D₆) δ 134.1, 131.0, 119.1, 58.4, 34.2, 15.1, 11.8, 4.7, −2.1.

EXAMPLE 86 Preparation of(Tert-butylamido)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdimethyl

[0259] A solution of 0.5000 g (1.215 mmol)(tert-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silanezirconiumdichloride in 35 mL ether was cooled to −40° C. To this was slowly added1.41 mL methyl lithium solution (1.72 M, 2.43 mmol). The reactionmixture was allowed to stir at room temperature for several hours. Thesolvent was removed and the residue was extracted with pentane andfiltered. The filtrate was concentrated and chilled to −40° C. Thecolorless crystals which formed were isolated by decanting away thesupernatant. Yield: 0.2215 g, 49.2% ¹H NMR (C₆D₆) δ 1.97, (s, 6H), 1.91(s, 6H), 1.40 (S, 9H), 0.46 (s, 6H), 0.00 (s, 6H). ¹³C NMR (C₆D₆) δ130.2, 125.3, 95.7, 54.7, 35.4, 34.0, 13.9, 10.9, 6.2.

EXAMPLE 87 Preparation of(tert-butylamido)dimethyl(η⁵-cyclopentadienyl)silanetitanium dichloride

[0260] (Chloro)(cyclopentadienyl)(dimethyl)silane

[0261] A solution of 149 g (1.16 mol) Me₂SiCl₂ in 750 mL diethyl etherwas cooled to −78° C. Solid sodium cyclopentadienide (30 g, 0.341 mol)was added via a powder addition funnel over a period of 1.5 hours. Thereaction mixture was allowed to warm to room temperature and was stirredfor 16 hours. The ether and some Me₂SiCl₂ were distilled out, thenexhaustive vacuum distillation removed the remaining ether, Me₂SiCl₂ andthe product from the NaCl formed in the reaction. The product afterfractionation was obtained in good yield as a light-yellow oil. MassSpec: m/e 158 (16%).

[0262] (Tert-butylamino)(cyclopentadienyl)(dimethyl)silane

[0263] To a solution of 3.69 g (50.4 mmol) tert-butyl amine in 45 mL THFwas added 2.00 g (12.6 mmol) (chloro)(cyclopentadienyl)(dimethyl)silane.Precipitate formed quickly. The slurry was stirred for several days,then the amine hydrochloride was filtered off and the solvent wasremoved under reduced pressure to give the product as a very paleyellowish oil. The yield was 2.069 g (84.2%). Mass spec: m/e 195 (6%).¹H and ¹³C NMR show the presence of several cyclopentadiene isomers.

[0264] Dilithium (tert-butylamido)(cyclopentadienyl)(dimethyl)silane

[0265] To a solution of 1.500 g (7.69 mmol)(tertbutylamido)(cyclopentadienyl)(dimethyl)silane in 60 mL ether wasslowly added 6.21 mL of a 1.72 M (10.68 mmol) ether solution ofmethyllithium, then 1.81 mL of 2.6 M (4.706 mmol) butyllithium in mixedalkane solvent (15.39 mmol total alkyllithiums). The resulting slurrywas stirred overnight, then filtered and washed with pentane, then driedunder reduced pressure to give the product as a white powder. The yieldwas 1.359 g (85.2%). ¹H NMR (THF d-8) δ 5.96 (t, 2H), 5.87 (t, 2H), 1.10(s, 9H), 0.05 (s, 6H). ¹³C NMR (THF d-8) d 114, 105.2, 103.5, 52, 38.3,7.3.

[0266] (tertbutylamido)dimethyl(η⁵-cyclopentadienyl)silane titaniumdichloride

[0267] 0.7000 g (3.38 mmol) Dilithium(tertbutylamido)(cyclopentadienyl)(dimethyl)silane and 1.128 g (3.38mmol) TiCl₄.(THF)₂ were combined in a flask with 75 mL toluene. Theresulting yellow slurry turned muddy red-brown within a few hours. Thereaction mixture was stirred for several days then the red solution wasfiltered and the solvents removed under reduced pressure. Thecrystalline material formed was slurried with pentane and filtered toremove the soluble red impurity from the brown product. The yield was0.5369 g (50.9%). ¹H NMR (C₆D₆) δ 6.60 (t, 2H), 6.07 (t, 2H), 1.38 (s,9H), 0.18 (s, 6H). ¹³C NMR (C₆D₆) δ 126.3, 125.6, 110.0,63.7, 32.2,−0.2.

[0268] Polymerization

[0269] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 3102kPa (450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurizedto 3447 kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was28.1 g, Mw=108,000, Mw/Mn=3.22, density=0.9073, melt index=2.92.

EXAMPLE 88 Preparation of(Tert-butylamido)dimethyl(η⁵-cyclopentadienyl)silanezirconium dichloride

[0270] To 0.6747 g (2.90 mmol) ZrCl₄ in a flask was slowly added 4 mLdiethyl ether, then 4 mL THF. The excess solvents were removed undervacuum to yield a solid which was broken up to a powder. The solid wascombined with 0.6008 g (2.90 mmol) dilithium(tert-butylamido)(cyclopentadienyl)(dimethyl)silane (prepared accordingto the technique of Example 87 and 75 mL toluene. The resulting slurrywas stirred for several days after which the colorless solution wasfiltered, the solvent removed under reduced pressure and the residue wasslurried in pentane. The product was collected on a frit and dried underreduced pressure. Yield was 0.6186 g (60.0%). ¹H NMR (C₆D₆) δ 6.43 (t,2H), 6.08 (t, 2H), 4.17 (br s, 6H), 1.27 (s, 9H), 1.03 (br s, 6H), 0.22(s, 6H). ¹³C NMR (C₆D₆) δ 122.0, 121.4, 109.5, 78, 57.2, 32.8, 25.2,0.7. The structure was shown by x-ray crystallography to be dimeric(bridging chlorides) in the solid state.

EXAMPLE 89 Preparation of (Anilido)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride

[0271] (Anilido)(dimethyl)(tetramethylcyclopentadienyl)silane

[0272] To a solution of 1.500 g (6.98 mmol)(chloro)(dimethyl)(tetramethylcyclopentadienyl)silane in 50 mL THF wasslowly added 0.6911 g (6.98 mmol) lithium anilide. Monitoring by GCindicated the reaction was incomplete. Additional lithium anilide (0.08g, 7.78 mmol total) was added. The reaction mixture was stirredovernight. The solvent was removed, the residue was extracted withpentane and filtered. The pentane was removed under reduced pressure togive the product as a pale yellow oil. The yield was 1.875 g (99.2%).Mass spec. m/e 271 (13%). ¹H NMR (C₆D₆) δ 7.14 (m, 2H), 6.76 (t, 1H),6.60 (d, 2H), 3.08 (s, 1H), 3.04 (s, 1H), 1.89 (s, 6H), 1.79 (s, 6H),0.07 (s, 6H). ¹³C NMR (C₆D₆) δ 147.5, 136.3, 132.6, 129.6, 118.2, 116.9,55.0, 14.3, 11.3, −2.2.

[0273] Dilithium (anilido)(dimethyl)(tetramethylcyclopentadienyl)silane

[0274] To a solution of 1.875 g (6.91 mmol)(anilido)(dimethyl)(tetramethylcyclopentadienyl)silane in 50 mL etherwas slowly added 5.31 mL of 2.60 M (13.8 mmol) butyllithium in hexanesolvent. A small amount of precipitate formed, but then dissolved. Thereaction mixture was stirred overnight. The product appeared to havecollected as a thick viscous oil in the ether solution The solvent wasremoved under reduced pressure. The resulting white solid was slurriedin pentane, collected on a frit, washed with pentane and dried underreduced pressure to give the product as a white powder. The yield was1.943 g (99.3%).

[0275](Anilido)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0276] A slurry of 0.8025 g (2.333 mmol) dilithium(anilido)(dimethyl)(tetramethylcyclopentadienyl)silane and 0.9871 g(2.333 mmol) TiCl₄(THF)₂ in 70 mL toluene was stirred for several days.The red-brown reaction mixture was filtered and the solvent was removed.The solid was triturated in pentane and the product was collected on afrit and washed with cold pentane to remove a dark red oily material togive the product as a yellow-beige powder. Yield: 0.6400 g, 55.8%. ¹HNMR (C₆D₆) δ 7.32 (d, 2H), 7.18 (m, 2H), 6.85 (t, 1H), 2.02 (s, 6H),1.99 (s, 6H), 0.42 (s, 6H). ¹³C NMR (C₆D₆) δ 152.4, 141.9, 137.8, 129.3,124.4, 119.6, 105.3, 16.1, 13.0, 2.7.

[0277] Polymerization 1

[0278] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 3102kPa (450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurizedto 3447 kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was12.8 g, Mw=103,000, Mw/Mn=4.77, density=0.9387, melt index=6.37.

[0279] Polymerization 2 Ethylene/Styrene Copolymerization

[0280] The above polymerization procedure was substantially followedexcept that 900 mL of mixed alkane solvent, 184 mL of styrene, 345 kPadelta hydrogen, and 20 micromoles of [(C₅Me₄)SiMe₂(tert-butyl)]TiCl₂were used. The temperature of the reactor was 120° C. After 10 minutes,the contents were removed from the reactor, and 62.3 g of polymer wasrecovered. The melt index was 3.68.

EXAMPLE 90 Preparation of (Anilido)(dimethyl)(tetramethyl-η⁵-cyclopenta-dienyl)silanezirconium dichloride

[0281] To 0.6905 g (2.963 mmol) ZrCl₄ in a flask was slowly added 3 mLdiethyl ether, then 4 mL THF. The excess solvents were removed undervacuum to yield a solid which was broken up to a powder. The solid wascombined with 0.8044 g (2.963 mmol) dilithium(anilido)(dimethyl)(tetramethyl-η⁵-cyclopenta-dienyl)silane and 70 mLtoluene. Within minutes the slurry color became pale yellow-green. Theslurry was stirred for several days after which time the solution wasfiltered, the solvent removed under reduced pressure and the residue wasslurried in pentane. The very pale yellowish product was collected on afrit and dried under reduced pressure. ¹H NMR (C₆D₆) δ 7.21 (t, 2H), 7.1(t, 1H), 6.97 (m, 2H), 2.50 (s, 3H), 2.46 (s, 3H), 1.87 (s, 3H), 1.85(s, 3H), 0.53 (s, 3H), 0.40 (s, 3H).

EXAMPLE 91 Preparation of (p-Toluidino)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dichloride

[0282] (p-Toluidino)(dimethyl)(tetramethylcyclopentadienyl) silane

[0283] To a solution of 2.000 g (9.302 mmol)(chloro)(dimethyl)(2,3,4,5-tetramethylcyclopentadienyl)silane in 70 mLTHF was slowly added 1.259 g (9.302 mmol) lithium p-toluidide (0.3 etheradduct by ¹HNMR). The reaction mixture was stirred overnight. Monitoringby GC indicated the reaction was incomplete. Additional lithiump-toluidide was added in small lots (0.725 g, 14.7 mmol total). Thesolvent was removed, the residue was extracted with pentane andfiltered. The pentane was removed under reduced pressure to give theproduct as a yellow oil. The yield was 2.456 g (92.5%). Mass spec. m/e285 (22%). ¹H NMR (C₆D₆) δ 6.96 (d, 2H), 6.57 (d, 2H), 3.07 (s, 1H),3.01 (s, 1H), 2.17 (s, 3H), 1.91 (s, 6H), 1.80 (s, 6H), 0.08 (s, 6H).¹³C NMR (C₆D₆) δ 145.0, 136.2, 132.7, 130.2, 126.9, 116.9, 55.2, 20.5,14.3, 11.3, −2.2.

[0284] Dilithium (p-toluidino)(dimethyl)(tetramethylcyclopentadienyl)silane

[0285] To a solution of 2.233 g (7.82 mmol)(p-toluidino)(dimethyl)(tetramethylcyclopentadienyl)silane in 65 mLether was slowly added 6.17 mL of 2.60 M (16.0 mmol) butyllithium inmixed C₆ alkane solvent. The precipitate-free reaction mixture wasstirred overnight. The solvent was removed under reduced pressure. Theresulting white solid was slurried in pentane, collected on a frit,washed with pentane and dried under reduced pressure to give the productas a white powder. The yield was 2.34 g (100%). ¹H NMR (THF 6-8) d 6.42(d, 2H), 6.18 (d, 2H), 2.09 (s, 6H), 2.01 (s, 3H), 1.94 (s, 6H), 0.36(s, 6H). ¹³C NMR (THF 6-8) δ 160.8, 129.1, 121.3, 115.9, 115.2, 112.2,106.2, 20.8, 14.7, 11.7, 5.2.

[0286](p-Toluidino)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0287] A slurry of 1.000 g (3.363 mmol) dilithium(p-toluidino)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silane and 1.123g (3.363 mmol) TiCl₄(THF)₂ in 70 mL toluene. The reaction mixture wasstirred several days, then filtered and the solvent was removed. Theresulting solid was slurried in pentane and the product was collected ona frit and dried under reduced pressure. The yield of olive-brown powderwas 0.7172 g, 53.0%. ¹H NMR (C₆D₆) δ 7.26 (d, 2H), 7.01 (d, 2H), 2.08(s, 3H), 2.04 (s, 6H), 2.00 (s, 6H), 0.45 (s, 6H). ¹³C NMR (C₆D₆) δ150.3, 141.7, 137.5, 133.9, 130.0, 129.7, 119.6, 21.0, 20.6, 16.4, 16.0,13.3, 12.8, 2.8, 2.6.

[0288](p-Toluidino)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdichloride

[0289] To 0.7836 g (3.363 mmol) ZrCl₄ in a flask was slowly added 3 mLdiethyl ether, then 4 mL THF. The excess solvents were removed undervacuum to yield a solid which was broken up to a powder. The solid wascombined with 1.000 g (3.363 mmol) dilithium(p-toluidino)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silane and 70 mLtoluene. The slurry was stirred for several days. The initiallyyellowish slurry turned brownish. The yellow solution was filtered, thesolvent removed under reduced pressure and the solid was slurried inpentane. The pale yellow product was collected on a frit and dried underreduced pressure. The yield was 0.8854 g (59.1%). ¹H NMR (C₆D₆) δ 7.06(d, 2H), 6.87 (d, 2H), 2.50 (s, 3H), 2.47 (s, 3H), 2.21 (s, 3H), 1.89(s, 3H), 1.88 (s, 3H), 0.51 (s, 3H), 0.41 (s, 3H). The structure wasshown by x-ray crystallography to be a LiCl-containing dimer withbridging chlorides.

EXAMPLE 92 Preparation of (Benzylamido)dimethyl (tetramethyl-ηhu5-cyclopentadienyl) silanetitanium dichloride

[0290] (Benzylamino)dimethyl(tetramethylcyclopenta-dienyl)silane

[0291] To a solution of 1.000 g (4.651 mmol)(chloro)(dimethyl)(tetramethylcyclopentadienyl)silane in 70 mL ether wasslowly added 0.526 g (4.651 mmol) lithium benzylamide. The reactionmixture was stirred overnight, then the solvent was removed, the residuewas extracted with pentane and filtered. The pentane was removed underreduced pressure to give the product as a pale yellow oil. The yield was1.234 g (93.3%). Mass spec. m/e 285 (18%). ¹H NMR (C₆D₆) δ 7.0-7.24 (m,5H), 3.71 (d, 2H), 2.73 (br s, 1H), 1.88 (s, 6H), 1.76 (s, 6H), 0.43 (brt, 1H), −0.07 (s, 6H). ¹³C NMR (C₆D₆) δ 144.5, 135.7, 132.0, 128.5,127.3, 126.7, 56.7, 46.4, 14.6, 11.4, −2.3.

[0292] Dilithium(benzylamido)dimethyl(tetramethyl-cyclopentadienyl)silane

[0293] To a solution of 1.091 g (3.836 mmol)(benzylamino)(dimethyl)(tetramethylcyclopenta-dienyl)silane in 70 mLether was slowly added 3.1 mL of 2.60 M (8.06 mmol) butyl lithium inmixed C₆ alkane solvent. A pale pink color forms along with precipitate.The reaction mixture was stirred overnight. The solvent was removedunder reduced pressure. The resulting solid was slurried in pentane,collected on a frit, washed with pentane and dried under reducedpressure to give the product as a very pale pink powder. The yield was1.105 g (96.9%). ¹H NMR (THF d-8) d 7.15 (m, 4H), 7.00 (t, 1H), 4.02 (s,2H), 2.04 (s, 6H), 1.79 (s, 6H), −0.15 (s, 6H). ¹³C NMR (THF d-8) d152.1, 128.1, 127.9, 125.0, 115.8, 111.9, 108.3, 54.0, 15.0, 11.2, 4.6.

[0294](Benzylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0295] A slurry of 0.5052 g (1.699 mmol) dilithium(benzylamido)(dimethyl)(tetramethyl-η⁵-cyclopentadienyl)silane and0.5673 g (1.699 mmol) TiCl₄(THF)₂ in 40 mL toluene was stirred forseveral days. The dark green-brown reaction mixture was filtered and thesolvent was removed. The dark oily residue was slurried in pentane andthe product was collected on a frit and washed with cold pentane toremove a dark oily material to give the product as a greenish yellowpowder. Yield: 0.2742 g (40.1%). ¹H NMR (C₆D₆) δ 7.19 (m, 2H), 7.02 (m,3H), 5.37 (s, 2H), 1.99 (s, 6H), 1.98 (s, 6H), 0.03 (s, 6H). ¹³C NMR(C₆D₆) δ 141.4, 140.9, 135.8, 129.0, 128.8, 126.9, 126.6, 126.3, 111.6,103.6, 59.3, 15.6, 12.4, 1.7.

[0296] Polymerization

[0297] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 3102kPa (450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurizedto 3447 kPa (500 psig). to give a delta pressure of 345 kPa (50 psi).The hydrogen was expanded into the reactor, and 10 micromoles of theabove complex was added to begin the polymerization. Ethylene wasprovided on demand at 3102 kPa (450 psig). After 10 minutes, thesolution was drained from the reactor into a container which had a smallamount of antioxidant. The polymer was dried under vacuum. The polymeryield was 14.4 g, Mw=Mw/Mn 5.0, melt index=251, density=0.9690.

EXAMPLE 93 Preparation of (Benzylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dichloride

[0298] In a flask were combined 0.3930 g (1.687 mmol) ZrCl₄, 0.5015 g(1.687 mmol) dilithium(benzylamido)dimethyl(tetramethyl-η⁵-cyclopenta-dienyl)silane and 40 mLtoluene. The brownish yellow slurry was stirred for several days thenfiltered and the solvent was removed under reduced pressure. The moisttan residue was slurried in pentane and the product was collected on afrit and dried under reduced pressure. Yield of the off-white tanproduct: 0.2873 g (38.2%). ¹H NMR (C₆D₆) δ 7.51 (d, 2H), 7.23 (t, 2H),7.09 (t, 1H), 5.48 (d, 1H), 5.00 (d, 1H), 2.45 (s, 6H), 2.05 (s, 3),2.01 (s, 3H), 0.34 (s, 3H), 0.20 (s, 3H). ¹³C NMR (C₆D₆) δ 145.2, 135.1,132.2, 131.8, 129.4, 129.0, 128.9, 128.8, 127.0, 126.6, 126.3, 106.6,57.2, 16.0, 15.6, 12.5, 11.8, 2.6.

EXAMPLE 94 Preparation of (Phenylphosphino)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride

[0299] (Phenylphosphino)(dimethyl)(tetramethylcyclopentadienyl)silane

[0300] To a solution of 1.500 g (6.983 mmol)(chloro)(dimethyl)(tetramethylcyclopentadienyl)silane in 55 mL THF wasslowly added 1.1248 g (7.665 mmol, excess added as GC monitoringindicated 1:1 reaction was incomplete) lithium phenylphosphide (0.4ether adduct by ¹H NMR spectroscopy). The reaction mixture was stirredseveral days, then the solvent was removed, the residue was extractedwith pentane and filtered. The pentane was removed under reducedpressure to give the product as a yellow oil. The yield was 1.985 g(98.5%).

[0301] Dilithium(phenylphosphido)dimethyl(tetramethylcyclopentadienyl)silane

[0302] To a solution of 1.858 g (6.451 mmol)(phenylphosphino)(dimethyl)(tetramethylcyclopentadienyl)sil ane in 65 mLether was slowly added 5.21 mL of 2.60 M (13.55 mmol) butyllithium inmixed C₆ alkane solvent with the formation of a yellowish precipitate.The reaction mixture was stirred overnight. The product was collected ona frit and washed with pentane, then dried under reduced pressure togive the product as a white powder. The yield (0.5 ether adduct by ¹HNMR spectroscopy) was 2.0845 g (95.8%).

[0303](Phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride

[0304] In a flask were combined 0.900 g (2.668 mmol) dilithium(phenylphosphido)(dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane (0.5ether adduct) and 0.8907 g (2.668 mmol) TiCl₄(THF)₂ with 75 mL toluene.The color instantly changed to deep green-black on addition of toluene.The reaction mixture was stirred for several days, then was filtered andthe solvent was removed. The dark residue was extracted with pentane andfiltered to leave a green-brown product on the frit (0.2477 g) and ablack glassy product on removal of the pentane from the filtrate.

[0305] Polymerization

[0306] The polymerization procedure of Examples 11-33 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 3102kPa (450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurizedto 3447 kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was14.4 g, Mw=27,700, Mw/Mn=5.0, melt index=251, density=0.9690.

EXAMPLE 95 Preparation of (Phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dichloride

[0307] To 0.6217 g (2.668 mmol) ZrCl₄ in a flask was slowly added 3 mLdiethyl ether. The excess solvent was removed under vacuum to yield asolid which was broken up to a powder. The solid was combined with0.9000 g (2.668 mmol) dilithium(phenylphosphido)dimethyl-(tetramethyl-η⁵-cyclopentadienyl)silane and 75mL toluene. The color changed to deep red-orange on addition of toluene.The reaction mixture was stirred for several days, then the orangesolution was filtered from a large quantity of dark insoluble materialand the solvent was removed. The residue was slurried with pentane andfiltered. A brown solid was collected on a frit and dried under reducedpressure.

EXAMPLE 96 Preparation of (Tert-butylamido)dimethyl(indenyl)silanetitanium dichloride

[0308] (Tert-butylamino)dimethyl(indenyl)silane

[0309] To a solution of 5.255 g (71.8 mmol) tert-butyl amine in 75 mLether was added 3.000 g (14.4 mmol) 9-(chlorodimethylsilyl)indene.Precipitate formed within a few minutes of the start of the addition.The slurry was stirred overnight, then the solvent was removed, theresidue was extracted with pentane and filtered. The pentane was removedunder reduced pressure to give the light-yellow oil product as a mixtureof two isomers. The yield was 3.313 g, (93.9%).

[0310] Dilithium (tert-butylamido)dimethyl(indenyl)silane

[0311] To a solution of 3.125 g (12.73 mmol)(tert-butylamino)dimethyl(indenyl)silane in 75 mL ether was slowly added10.28 mL of 2.60 M (26.73 mmol) butyl-lithium in mixed C₆ alkanesolvent. The color of the precipitate-free solution darkens slightly tobeige-orange. The reaction mixture was stirred several days, then thesolvent was removed. The fluffy, glassy material was slurried withpentane. The powder clumps together. The pentane was decanted and thewashing procedure was repeated several times, then the solid was driedunder reduced pressure. The yield was 2.421 g (73.9%).

[0312] (Tert-butylamido)dimethyl(indenyl)silanetitanium dichloride

[0313] In a flask were combined 1.000 g (3.887 mmol) dilithium(tertbutylamido)(dimethyl)(indenyl)silane and 1.298 g (3.887 mmol)TiCl₄(THF)₂ with 70 mL toluene. A deep red color developed instantly.The reaction mixture was stirred three days, then filtered, and thesolvent was removed. The residue was extracted with pentane and filteredto give the product as a red microcrystalline material. The yield was0.4917 g (34.9%).

[0314] Polymerization

[0315] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of isopar-E, 200 mL of 1-octene and 5 mL of 15 percent MAOin toluene (1280 Al:Ti). The reactor was saturated with 3102 kPa (450psig) of ethylene, and a 75 mL tank of hydrogen was pressurized to 3447kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was14.8 g.

EXAMPLE 97 Preparation of (Tert-butylamido)dimethyl(indenyl)silanezirconium dichloride

[0316] To 0.9057 q (3.887 mmol) ZrCl₄ in a flask was slowly added 2 mLTHF. The excess THF was removed under vacuum to yield a solid which wasbroken up to a powder. 1.000 g (3.887 mmol) dilithium(tertbutylamido)dimethyl(indenyl)silane was added along with 70 mLtoluene. The resulting slurry was stirred for several days after whichthe solution was filtered and the solvent removed under reducedpressure. The residue was slurried in pentane, filtered and dried underreduced pressure. The yield of brown-biege product was 0.5668 g (36.0%).

EXAMPLE 98 Preparation of (Methylamido)dimethyl(tetramethyl-η⁵-cyclopenta-dienyl)silanetitanium dichloride

[0317] (Methylamino)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane

[0318] To a solution of 1.900 g (8.845 mmol)(chloro)(dimethyl)(tetramethylcyclopentadienyl)silane in 75 mL THF wasquickly added 0.3272 g (8.846 mmol) lithium methylamide. The clearsolution was stirred overnight, then additional lithium methylamide(0.008 g, 9.062 mmol total) was added as gas chromatography (GC)indicated the reaction was incomplete and the solution was stirredovernight again. The solvent was removed, the residue was extracted withpentane and filtered, and the pentane was removed under reduced pressureto give the product as a very pale yellow oil. The yield was 1.698 g(91.7%). Mass spec. m/e 209 (13 percent). ¹H NMR (C₆D₆): δ 2.82 (s, 1H),2.33 (d, J=6.6 Hz, 3H), 1.95 (s, 6H), 1.83 (s, 6H), −0.04 (s, 6H). ¹³CNMR (C₆D₆: δ 135.4, 132.7, 56.1, 27.8, 14.0, 11.0, −3.5.

[0319] Dilithium(methylamido)dimethyl(tetramethylcyclopentadienyl)silane

[0320] To a solution of 1.563 g (7.463 mmol)(methylamino)(dimethyl)(tetramethylcyclopentadienyl) silane in about 65mL ether/pentane (1:1) was slowly added 6.03 mL of 2.60 M (15.7 mmol)butyllithium in mixed C₆ alkane solvent. The solution turned to a thicksyrup which broke down to a slurry. The reaction mixture was stirredovernight, then filtered. The solid was washed several times with ether,then with pentane, then dried under reduced pressure to give the productas a white powder. The yield was 1.883 g of a 0.25 ether adduct asdetermined by ¹H NMR spectroscopy. ¹H NMR (THF δ-8) δ 3.41 (q,J=7.0 Hz,1H), 2.45 (s, 3H), 2.01 (s, 6H), 1.93 (s, 6H), 1.11 (t, J=7.01, 0.5H),0.01-0.14 (br, 6H).

[0321](Methylamido)dimethyl(tetramethyl-η⁵-cyclopenta-dienyl)silanetitaniumdichloride

[0322] To a solution of 0.6708 g (2.597 mmol) dilithium(methylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silane in 80 mLTHF was added all at once 0.9623 g (2.597 mmol) TiCl₃(THF)₃. Thesolution immediately turned intense brown-orange. The reaction mixturewas stirred four days, then 1.861 g (12.98 mmol) AgCl was added. Theslurry was stirred several days after which the reaction mixture wasfiltered and the solvents were removed under reduced pressure. Theresidue was extracted with toluene, the dark orange-brown solution wasfiltered and the solvent was removed. After extraction with pentane andfiltration, the filtrate was concentrated to a light brown slurry in adark red solution. After cooling to −30° C., the bright yellow productwas collected on a frit, washed with pentane and dried under reducedpressure. The yield was 0.3168 g (37.4%). ¹H NMR (C₆D₆): 3.64 (s,3H),1.97 (s, 6H), 1.95 (s, 6H), 0.21 (s, 6H). ¹³C NMR (C₆D₆): δ 140.5,135.5, 103.0, 41.8, 15.5, 12.3, 0.6.

[0323] Polymerization

[0324] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 3102kPa (450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurizedto 3447 kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was30.2 g.

EXAMPLE 99 Preparation of (Methylamido)dimethyl(tetramethyl-η⁵-cyclopenta-dienyl)silanezirconium dichloride

[0325] In a flask 0.5705 g (2.448 mmol) ZrCl₄ and 0.6318 g (2.446 mmol)dilithium (methylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanewere combined with 75 mL toluene. The slurry was stirred for severaldays after which time the resulting pale green solution was filtered,and the solvent was removed under reduced pressure. The residue wasslurried in pentane, collected on a frit, washed with pentane and driedunder reduced pressure. The yield of very pale powder blue product was0.6162 g (68.2%). ¹H NMR (C₆D₆): δ 3.50 (s, 3H), 2.49 (s, 3H) 2.36 (s,3H), 2.14 (s, 3H), 2.10 (s, 3H), 0.46 (s, 3H), 0.43 (s, 3H).

EXAMPLE 100 Preparation of1-(Tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitaniumdichloride

[0326] Ethyl 2-(tetramethylcyclopentadienyl)acetate

[0327] A solution of 3.822 g (22.89 mmol) ethyl bromoacetate in 25 mLTHF was cooled to −78° C. and 3.000 g (20.80 g) sodiumtetramethylcyclopentadienide in 50 mL THF was slowly added to it. Theresulting slurry was allowed to warm to room temperature and was stirredovernight. The solvent was removed, the residue was extracted withpentane and filtered. The pentane was removed to give a mixture ofisomers. Yield was 3.733 g (86.3%). Mass spectra m/e 208 (41 percent).

[0328] 2-(Tetramethylcyclopentadienyl)tert-butyl acetamide

[0329] 16.35 mL of 2.00 M (32.7 mmol) trimethyl aluminum in toluene wasadded to 2.39 g (32.7 mmol) tert-butylamine in 50 mL toluene. Thesolution was stirred for 45 minutes, then 3.40 gethyl-2-tetramethylcyclopentadienyl acetate was added. The reactionmixture was stirred for several days while gently warming. After aqueousworkup the product amide was obtained as a mixture of three isomers asan orange semicrystalline paste. Mass spectra m/e 235 (21%).

[0330] 1-(tert-butylamino)-2-(tetramethylcyclopentadienyl)ethane

[0331] The amide mixture was dissolved in 120 mL ether and 0.830 g (21.8mmol) lithium aluminum hydride was added. The reaction mixture wasstirred overnight under gentle heating. Monitoring by GC indicated thereaction was incomplete. The ether was replaced by THF, more lithiumaluminumhydride was added and the solution was refluxed for severaldays. After aqueous workup three1-(tert-butylamino)-2-(tetramethylcyclopentadienyl)ethane isomers wereobtained. Mass spectra m/e 221 (11%).

[0332] Dilithium1-(tertbutylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethane

[0333] To a solution of 2.00 g (9.05 mmol)(tert-butylamino)-2-(tetramethylcyclopentadienyl)ethane isomers (67%1-(tertbutylamino)-2-(2,3,4,5-tetramethylcyclopentadi-2,4-enyl)ethane byGC, 1.34 g (6.06 mmol)) in 50 mL ether was slowly added 6.09 mL of 2.60M (15.8 mmol) butyllithium in mixed C₆ alkane solvent with formation ofa yellow precipitate. The reaction mixture was stirred three days, thenfiltered. The light yellow powder was washed several times with ether,then dried under reduced pressure. The yield was 0.7908 g (55.9%). ¹HNMR (THF d-8): δ 2.43 (br m, 4H), 1.85 (s, 6H), 1.83 (s, 6H), 1.00 (s,9H). ¹³C NMR (THF d-8): δ 109.5, 107.3, 106.3, 50.5, 45.4, 29.4, 28.2,20.2, 10.9, 10.8.

[0334]1-(Tert-butylamido)-2-(tetramethyl-1⁵-cyclopentadienyl)ethanediyltitaniumdichloride

[0335] In a flask 0.3650 g (1.565 mmol) dilithium1-(tert-butylamido)-2-(tetramethylcyclopentadienyl)ethane and 0.5799 g(1.565 mmol) TiCl₃(THF)₃ were combined with 60 mL THF. The solutionquickly turned green. The reaction mixture was stirred overnight, then1.121 g (7.82 mmol) AgCl was added. Within a few minutes the color beganto change to brownish orange. The slurry was stirred two days and thesolvents were removed under reduced pressure. The residue was extractedwith toluene, the solution was filtered and the solvent was removed. Theresidue was extracted with pentane, filtered, concentrated, and cooledto −30° C. The bright orange product was collected on a frit, washedwith a small amount of cold pentane and dried under reduced pressure.The yield was 0.1904 g (36.0%). ¹H NMR (C₆D₆): δ 4.01 (t, J=7.2, 2H),2.58 (t, J=7.2, 2H), 2.02 (s, 6H), 1.89 (s, 6H), 1.41 (s, 9H). ¹³c NMR(C₆D₆) δ 138.0, 129.3, 128.6, 69.1, 62.7, 28.6, 24.9, 13.0, 12.3.

[0336] Polymerization 1

[0337] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of isopar-E, 200 mL of 1-octene and 5 mL of 15 percent MAOin toluene (1280 Al:Ti). The reactor was saturated with 3102 kPa (450psig) of ethylene, and a 75 mL tank of hydrogen was pressurized to 3447kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was64.8 g, melt index=3.21, density=0.9262.

[0338] Polymerization 2

[0339] The above polymerization procedure was repeated excepting that0.95 micromoles of1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)-ethanediyltitaniumdichloride was added to begin the polymerization. The polymer yield was11.4 g, melt index<0.1, density=0.9119.

[0340] Polymerization 3

[0341] The above polymerization procedure was repeated excepting that2.5 micromoles of1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)-ethanediyltitaniumdichloride was added to begin the polymerization. In addition, 300 mL ofoctene and 900 mL of isopar was used, and no hydrogen was used. Thepolymer yield was 36.2 g, melt index=0.21, density=0.9190.

[0342] Polymerization 4

[0343] The conditions of above polymerization 1 were repeated exceptingthat the temperature was 90° C. and 345 kPa (50 psi) of hydrogen wasused. The polymer yield was 66.7 g, melt index=0.16.

EXAMPLE 101 Preparation of1-(Tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediylzirconiumdichloride

[0344] In a flask 0.3862 g (1.657 mmol) ZrCl₄ and 0.3866 g (1.657 mmol)dilithium[1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethane] werecombined with 50 mL toluene. After stirring several days, 1 mL THF wasadded and the slurry was stirred for an additional day after which timethe solution was filtered, and the solvent was removed under reducedpressure. The solid was slurried in pentane, collected on a frit, anddried under reduced pressure. Yield of pale yellow product was 0.6307 g(99.8%). ¹H NMR (C₆D₆): δ 2.75 (t of d, 1H), 2.38 (m, 2H), 2.11, (s, 6H)2.03 (s, 3H), 2.00 (s, 3H), 1.75 (t of d, 1H), 1.08 (s, 9H). ¹³C NMR(C₆D₆): δ 131.5, 128.7, 126.8, 126.5, 126.2, 56.9, 50.9, 27.9, 23.1,13.4, 13.2, 12.6, 12.5.

EXAMPLE 102 Terpolymer Polymerization

[0345] Mixtures of ethylene, styrene and another additionalpolymerizable monomer were polymerized using(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride complex and MAO cocatalyst in an amount to provide an atomicratio Al/Ti of 1000:1. Reaction conditions and results are contained inTable VI. TABLE VI In each case the cocatalyst was methylaluminoxane andthe metal complex was (tert-butylamido)dimethyl-(tetramethyl-η⁵-cyclopentadienyl)titanium dichloride.. mg T SolventEthylene Styrene Olefin Time Yield mol % mol % Run (complex) (° C.)(mL)^(a) (kPa) (mL) (g) (hr) (g) Styrene Olefin M_(w) M_(w)/M_(n) 1 1.890 I (670) 1517 38 butene 0.5 51 2.3 6.6 141,00 2.9 2 1.9 90 I (630) ″76 butene (9) 0.5 45 3.4 4.5 155,00 2.4 3 1.9 90 I (455) ″ 250 butene(5) 0.5 70 7.2 3.2 153,00 2.4 4 2.2 90 T (40) 1241 133 Vinyl- 2.0 3722.4 <1 39,000 1.7 BCB (1.5)^(b)

EXAMPLE 103 Slurry Polymerization

[0346] The following example demonstrates the use of a catalyst of thepresent invention under slurry conditions. The procedure of Examples11-32 was substantially followed, excepting that the reaction was rununder conditions where the polymer was insoluble in the reaction mediumand precipitated from the reaction mixture as it formed. The temperaturewas 70° C., 10 mL of octene, 1190 mL of mixed alkane solvent, and 5 mLof 15 percent MAO in toluene (1280 Al:Ti) were used. After 20 minutes,the reactor was drained to give 4.6 g of polymer. Additional solvent wasadded to the reactor and heated to 170° C. to remove the polymer thathad formed long filaments and wound around the stirrer. The melt indexwas 0.28.

EXAMPLE 104 Preparation of (Tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium(III) Chloride

[0347] In the drybox, 0.24 g of TiCl₃(THF)₃ and 0.33 g ofMe₄C₅SiMe₂N-t-BuMg₂Cl₂(THF)₂ were mixed. 15 mL Of THF was added,resulting in a deep purple color. After 30 minutes the volatilematerials were removed under reduced pressure to leave a dark solid.Toluene (15 mL) was added, the solution filtered, and the toluene wasremoved under reduced pressure to leave a red-purple powder, 0.22 g.

[0348] Polymerization

[0349] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane solvent, 200 mL of 1-octene and 5 mL of 15percent MAO in toluene (1280 Al:Ti). The reactor was saturated with 3102kPa (450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurizedto 3447 kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of the abovecomplex was added to begin the polymerization. Ethylene was provided ondemand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was55.1 g, melt index=1.71.

EXAMPLE 105

[0350] The polymerization procedure of Examples 11-32 was substantiallyfollowed. The reaction temperature was 130° C. The reactor was filledwith 1000 mL of mixed alkane, 200 mL of 1-octene and 5 mL of 15 percentMAO in toluene (1280 Al:Ti). The reactor was saturated with 3102 kPa(450 psig) of ethylene, and a 75 mL tank of hydrogen was pressurized to3447 kPa (500 psig) to give a delta pressure of 345 kPa (50 psi). Thehydrogen was expanded into the reactor, and 10 micromoles of(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride was added to begin the polymerization. Ethylene was providedon demand at 3102 kPa (450 psig). After 10 minutes, the solution wasdrained from the reactor into a container which had a small amount ofantioxidant. The polymer was dried under vacuum. The polymer yield was76.4 g, Mw=56,700, Mw/Mn=4.5, density=0.8871, melt index (I₂)=10.13.

EXAMPLE 106

[0351] The polymerization procedure of Example 105 was substantiallyfollowed except that the temperature was 80° C., the amount of catalystused was 2.5 micromoles, the amount of 1-octene used was 250 mL, and theamount of mixed alkane solvent used was 950 mL. The reaction was allowedto proceed for 1 hour. The polymer yield was 51.1 g. The melt index was0.11.

EXAMPLE 107 Preparation of (Tert-butylamido)dimethyl(tetramethylcyclopentadienyl)silanehafnium dichloride

[0352] In the drybox, 0.50 g of HfCl₄ was suspended in 10 mL of toluene.10 mL Of THF was added, the slurry was stirred for 5 minutes, and 0.77 gof Me₄C₅SiMe₂N-t-BuMg₂Cl₂(THF)₂ was added. THe solution was heated toreflux. After 30 minutes, the solution was cooled, and the volatilematerials were removed under reduced pressure. Pentane (20 mL) wasadded, the solution was filtered, and the pentane was removed underreduced pressure to leave a white solid. This solid was washed with asmall quantity of pentane to yield 0.077 g (10%) of a white solid, ¹HNMR (C₆D₆): δ 2.08 (6H), 1.30 (9H), 0.44 (6H).

[0353] When ethylene was polymerized substantially according to theprocedure of Example 7, a small amount of polyethylene was recovered.

COMPARATIVE 1

[0354] The polymerization procedure of Example 105 was substantiallyfollowed except that the catalyst waspentamethylcyclopentadienyltitanium trichloride. The polymer yield was4.6 g.

COMPARATIVE 2

[0355] The polymerization procedure of Example 97 was substantiallyfollowed except that the catalyst was(tert-butylamido)pentamethyl-η⁵-cyclopentadienyltitanium dichloride (¹HNMR (C₆D₆): δ 2.07 (s, 1H), 1.88 (s, 15H), 1.35 (s, 9H). ¹³C NMR (C₆D₆):δ 61.0, 31.3, 12.6). The polymer yield was 2.0 g.

COMPARATIVE 3

[0356] The polymerization procedure of Example 105 was substantiallyfollowed except that the catalyst wasbis(tert-butylamido)dimethylsilanetitanium dichloride. No polymer wasobserved after 10 minutes of reaction.

COMPARATIVE 4

[0357] The polymerization procedure of Example 105 was substantiallyfollowed except that the catalyst was dicyclopentadienylzirconiumdichloride. The polymer yield was 109.0 g, Mw=16,300, Mw/Mn=3.63, meltindex ASTM D-1238 Procedure A, condition E, I₂, was greater than 1,000indicating a very low molecular weight polymer.

COMPARATIVE 5

[0358] The polymerization procedure of Example 105 was substantiallyfollowed except that the catalyst was dicyclopentadienyltitaniumdichloride. The polymer yield was 7.3 g, melt index, ASTM D-1238Procedure A, condition E, I₂, was greater than 1,000 indicating a verylow molecular weight polymer.

1. A process for preparing a metal coordination complex of the formula:

wherein (a) M is selected from the group consisting of titanium,zirconium, and hafnium; (b) Cp* is selected from the group consisting ofcyclopentadienyl and R″_(m)-substituted cyclopentadienyl, bound in an η⁵bonding mode to M, wherein R″ is independently selected from the groupconsisting of alkyl of up to 20 carbon atoms and aryl of up to 20 carbonatoms and two adjacent R″ groups may join to form a ring and m is 1 to4; (c) Z is selected from the group consisting of CR′₂, CR′₂CR′₂, SiR′₂,and SiR′₂SiR′₂, wherein each R′ is independently selected from the groupconsisting of alkyl of up to 20 carbon atoms, aryl of up to 20 carbonatoms, and mixtures thereof of up to 20 carbon atoms; (d) Y is NR or PR,wherein R is selected from the group consisting of alkyl of up to 20carbon atoms, aryl of up to 20 carbon atoms, and mixtures thereof of upto 20 carbon atoms; (e) X is, independently each occurrence, selectedfrom the group consisting of hydride, halide, alkyl of up to 30 carbonatoms, aryl of up to 30 carbon atoms, aryloxy of up to a total of 30carbon and oxygen atoms, alkoxy of up to a total of 30 carbon and oxygenatoms, cyanide, aide, acetylacetonate, norbornyl, and benzyl; and (f) nis 2, said process comprising the steps of contacting a metal compoundof the formula MX_(n+2), or a coordinated adduct thereof with adianionic salt compound corresponding to the formula:(L^(+x))_(y)(Cp*-Z-Y)⁻² or ((LX″)^(+x))_(y)(Cp*-Z-Y)⁻² wherein: L is ametal of Group 1 or 2 of the Periodic Table of the Elements; X″ isfloro, chloro, bromo, or iodo; x and y are either 1 or 2 and the productof x and y equals 2; M, X, Cp*, n, Z and Y are as previously defined, ina non-coordinating, non-polar solvent; and recovering the resultingproduct.
 2. A process for preparing a metal coordination complex of theformula:

wherein (a) M is selected from the group consisting of titanium,zirconium, and hafnium; (b) Cp* is selected from the group consisting ofcyclopentadienyl and R″_(m)-substituted cyclopentadienyl, bound in an η⁵bonding mode to M, wherein R″ is independently selected from the groupconsisting of alkyl of up to 20 carbon atoms and aryl of up to 20 carbonatoms and two adjacent R″ groups may join to form a ring and m is 1 to4; (c) Z is selected from the group consisting of CR′₂, CR′₂CR′₂, SiR′₂,and SiR′₂SiR′₂, wherein each R′ is independently selected from the groupconsisting of alkyl of up to 20 carbon atoms, aryl of up to 20 carbonatoms, and mixtures thereof of up to 20 carbon atoms; (d) Y is NR or PR,wherein R is selected from the group consisting of alkyl of up to 20carbon atoms, aryl of up to 20 carbon atoms, and mixtures thereof of upto 20 carbon atoms; (e) X is, independently each occurrence, selectedfrom the group consisting of hydride, halide, alkyl of up to 30 carbonatoms, aryl of up to 30 carbon atoms, aryloxy of up to a total of 30carbon and oxygen atoms, alkoxy of up to a total of 30 carbon and oxygenatoms, cyanide, aide, acetylacetonate, norbornyl, and benzyl; and (f) nis 2, said process comprising the steps of contacting a metal compoundof the formula MX_(n+1), or a coordinated adduct thereof with adianionic salt compound corresponding to the formula:(L^(+x))_(y)(Cp*-Z-Y)⁻² or ((LX″)^(+x))_(y)(Cp*-Z-Y)⁻² wherein: L is ametal of Group 1 or 2 of the Periodic Table of the Elements; X″ isfloro, chloro, bromo, or iodo; x and y are either 1 or 2 and the productof x and y equals 2; M, X, Cp*, n, Z and Y are as previously defined, ina non-coordinating, non-polar solvent; contacting the resulting productwith a noninterfering oxidizing agent to raise the oxidation state ofthe metal, and recovering the resulting product.
 3. The process ofclaims 2 wherein the noninterfering oxidizing agent is AgCl.
 4. Theprocess according to any one of claims 1-3 wherein the non-coordinating,non-polar solvent is toluene.
 5. The process according to any one ofclaims 1-3 wherein M is titanium.
 6. The process according to claim 4wherein M is titanium.